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EP3049461A1 - Thermoplastic composition, in particular for photovoltaic modules - Google Patents

Thermoplastic composition, in particular for photovoltaic modules

Info

Publication number
EP3049461A1
EP3049461A1 EP14784502.8A EP14784502A EP3049461A1 EP 3049461 A1 EP3049461 A1 EP 3049461A1 EP 14784502 A EP14784502 A EP 14784502A EP 3049461 A1 EP3049461 A1 EP 3049461A1
Authority
EP
European Patent Office
Prior art keywords
composition
polymer
polyamide
weight
composition according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP14784502.8A
Other languages
German (de)
French (fr)
Other versions
EP3049461B1 (en
Inventor
Grégoire AUSSEDAT
Dominique Jousset
Stéphane Bizet
Jean-Jacques Flat
Samuel Devisme
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Arkema France SA
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Filing date
Publication date
Application filed by Arkema France SA filed Critical Arkema France SA
Publication of EP3049461A1 publication Critical patent/EP3049461A1/en
Application granted granted Critical
Publication of EP3049461B1 publication Critical patent/EP3049461B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01B—SOIL WORKING IN AGRICULTURE OR FORESTRY; PARTS, DETAILS, OR ACCESSORIES OF AGRICULTURAL MACHINES OR IMPLEMENTS, IN GENERAL
    • A01B39/00—Other machines specially adapted for working soil on which crops are growing
    • A01B39/12—Other machines specially adapted for working soil on which crops are growing for special purposes, e.g. for special culture
    • A01B39/16—Other machines specially adapted for working soil on which crops are growing for special purposes, e.g. for special culture for working in vineyards, orchards, or the like ; Arrangements for preventing damage to vines
    • A01B39/163—Other machines specially adapted for working soil on which crops are growing for special purposes, e.g. for special culture for working in vineyards, orchards, or the like ; Arrangements for preventing damage to vines comprising rotating tools
    • A01B39/166—Other machines specially adapted for working soil on which crops are growing for special purposes, e.g. for special culture for working in vineyards, orchards, or the like ; Arrangements for preventing damage to vines comprising rotating tools actively driven
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01B—SOIL WORKING IN AGRICULTURE OR FORESTRY; PARTS, DETAILS, OR ACCESSORIES OF AGRICULTURAL MACHINES OR IMPLEMENTS, IN GENERAL
    • A01B39/00—Other machines specially adapted for working soil on which crops are growing
    • A01B39/12—Other machines specially adapted for working soil on which crops are growing for special purposes, e.g. for special culture
    • A01B39/18—Other machines specially adapted for working soil on which crops are growing for special purposes, e.g. for special culture for weeding
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/049—Protective back sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
    • Y02P60/12—Technologies relating to agriculture, livestock or agroalimentary industries using renewable energies, e.g. solar water pumping

Definitions

  • the subject of the invention is a thermoplastic composition
  • a thermoplastic composition comprising at least a first particular polyolefin associated with a second polyamide grafted polyolefin whose grafts exhibit a glass transition temperature, or melting temperature, of less than 160 ° C.
  • the present invention also relates to the use of this composition in a photovoltaic module, more precisely in one or more of the layers forming such a module, more particularly in the encapsulating layer.
  • a photovoltaic module includes a "photovoltaic cell", this cell being capable of transforming light energy into electricity.
  • the structure of a photovoltaic module conventionally comprises three layers, a central layer housing the photovoltaic cells having photoelectric properties, surrounded on both sides by a protective layer.
  • the central layer is called classically encapsulating while the protective layers are called “frontsheet” transparent layer intended to allow the passage of solar rays, and “backsheet” layer to be the most waterproof / hermetic possible.
  • thermoplastic materials In general, photovoltaic modules being placed outside and in extreme environments, they undergo constant stress and aggression. Finally, the properties of the thermoplastic materials used must to guarantee a long-term preservation of the module's photoelectric properties, in other words without suffering any significant degradation.
  • thermoplastic materials include, in particular, excellent creep resistance at 100 ° C. or higher, good optical properties, good durability properties in moist heat and under UV (Ultra Violet), good electrical properties, low moisture recovery and excellent barrier properties.
  • polyolefin grafted polyamide composition (polyamide graft attached to the main chain) is known.
  • Such compositions are described in the documents of the applicant FR 2918150 or EP 2196489. It has even already been envisaged to mix such polyamide graft polyolefins with a polyolefin, especially in WO 0228959 in the name of the applicant.
  • composition according to the present invention while retaining mechanical, thermomechanical, optical, electrical, quite satisfactory properties, fills the last deficiencies that can present these thermoplastic materials otherwise extremely powerful, namely that this composition has a recovery. at low water, or very low, and degradation over time (electrical resistivity drop) particularly improved.
  • thermoplastic composition comprising at least one mixture of three polymers, wherein:
  • the first polymer present in the composition between 10% and 70% by weight, consists of a polyamide graft polymer having a polyolefin trunk containing a residue of at least one unsaturated monomer (X) and a plurality of polyamide grafts, in which :
  • the polyamide grafts are attached to the polyolefin trunk by the remainder of the unsaturated monomer (X) comprising a function capable of reacting by a condensation reaction with a polyamide having at least one amine end and / or at least one carboxylic acid end,
  • the polyamide grafts represent from 10% to 60%, preferably from 15% to 55%, by weight of said polyamide graft polymer,
  • the second polymer present in the composition between 10% and 90% by weight, consists of a copolymer of ethylene and a non-reactive or non-functional comonomer whose flexural modulus of elasticity is less than 250 MPa at 23 ° C and has a crystalline melting point of between 60 ° C and 120 ° C,
  • the third polymer present in the composition, between 3% and 45% by weight of said composition, consisting of a functionalized polyolefin comprising a copolymer of at least one alpha-olefin, such as ethylene or propylene, with at least a comonomer bearing a reactive function, and at least one other comonomer not carrying a reactive function, chosen from an alpha-olefin different from the aforesaid alpha-olefin, a diene, an unsaturated carboxylic acid ester, and a vinyl ester, carboxylic acid, a dicarboxylic acid anhydride such as maleic anhydride,
  • a functionalized polyolefin comprising a copolymer of at least one alpha-olefin, such as ethylene or propylene, with at least a comonomer bearing a reactive function, and at least one other comonomer not carrying a reactive function, chosen from an alpha-olefin different
  • the polyamide grafts of the above-mentioned first polymer have a glass transition temperature and a melting temperature of less than or equal to 160 ° C,
  • the level of the polyamide grafts of said first polymer is from 3% to 15%, preferably from 5% to 12.5%, by weight of the thermoplastic composition.
  • the second polymer will consist of a copolymer of ethylene and an alkyl (meth) acrylate.
  • the third polymer is an ethylene - acrylic ester - glycidyl methacrylate or ethylene - acrylic ester - maleic anhydride copolymer.
  • the third polymer is present between 10% and 30% by weight of the composition.
  • the molar mass in number of the aforesaid polyamide grafts of the aforesaid graft polymer is in the range of 1000 to 10000 g / mol.
  • the number of monomer (X) attached to the polyolefin trunk is greater than or equal to 1.3 and / or less than or equal to 20.
  • the aforesaid first polymer is present between 10% and 50% by weight of the composition.
  • the polyamide grafts of the first polymer consist of copolyamides chosen from copolyamides PA 6/11, PA6 / 12 and PA6 / 11/12.
  • the unsaturated monomer (X) of the first polymer is a maleic anhydride.
  • the second polymer present in the composition is between 40% and 70% by weight.
  • the composition according to the invention consists solely of the three aforesaid polymers.
  • the invention also relates to a film comprising the composition according to the invention as described above.
  • the invention also relates to a thermoplastic film of a photovoltaic module, said photovoltaic module comprising at least two layers, one of which forms the encapsulating layer, characterized in that the encapsulant layer comprises, preferably consists of, the thermoplastic composition as described above.
  • the encapsulant layer comprises adhesion promoters consisting of a non-polymeric, organic, crystalline or inorganic ingredient and more preferably semi-inorganic semi-organic antioxidants and / or anti-UV agents.
  • composition according to the invention is presented with for application a photovoltaic module, more particularly its encapsulant layer, but of course this composition may be envisaged for all other applications where such a composition is advantageously usable, especially in multilayer structures such as, for example, shoes, adhesive films or coatings, or fluid transport tubes.
  • a photovoltaic module more particularly its encapsulant layer
  • this composition may be envisaged for all other applications where such a composition is advantageously usable, especially in multilayer structures such as, for example, shoes, adhesive films or coatings, or fluid transport tubes.
  • the following description is given solely for illustrative and not limiting. Detailed description of the invention
  • the first polymer mentioned above is therefore a graft polymer, with between 10% and 70%>, preferably between 15% and 55%, by mass of polyamide grafts and a number of monomers (X) between 1.3 and 20.
  • polyolefin trunk it is a polymer comprising as monomer an ⁇ -olefin.
  • ⁇ -olefins having 2 to 30 carbon atoms are preferred.
  • ⁇ -olefin mention may be made of ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl- 1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, 1-dococene, 1-tetracocene, 1-hexacocene, 1-octacocene, and 1-octene -triacontène.
  • cycloolefins having from 3 to 30 carbon atoms, preferably from 3 to 20 carbon atoms, such as cyclopentane, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene; di and polyolefins, such as butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1 , 4-octadiene, 1,5-octadiene, 1,6-octadiene, ethylidenenorbornene, vinyl norbornene, dicyclopentadiene, 7-methyl-1,6-octa
  • ⁇ -olefin also includes styrene.
  • Propylene and especially ethylene are preferred as ⁇ -olefins.
  • This polyolefin may be a homopolymer when a single ⁇ -olefin is polymerized in the polymer chain. Examples include polyethylene (PE) or polypropylene (PP).
  • This polyolefin can also be a copolymer when at least two comonomers are copolymerized in the polymer chain, one of the two comonomers said the "first comonomer” being an ⁇ -olefin and the other comonomer, called “second comonomer”, is a monomer capable of polymerizing with the first monomer.
  • Dienes such as for example 1,4-hexadiene, ethylidene norbornene, butadiene
  • Unsaturated carboxylic acid esters such as, for example, alkyl acrylates or alkyl methacrylates grouped under the term alkyl (meth) acrylates.
  • the alkyl chains of these (meth) acrylates can have up to 30 carbon atoms. Mention may be made, as alkyl chains, of methyl, ethyl, propyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl and dodecyl.
  • Methyl, ethyl and butyl (meth) acrylates are preferred as unsaturated carboxylic acid esters.
  • vinyl esters of carboxylic acid As examples of vinyl esters of carboxylic acid, mention may be made of vinyl acetate, vinyl versatate, vinyl propionate, vinyl butyrate, or vinyl maleate. Vinyl acetate is preferred as the carboxylic acid vinyl ester.
  • the polyolefin trunk comprises at least 50 mol% of the first comonomer; its density may advantageously be between 0.91 and 0.96.
  • the preferred polyolefin trunks consist of an ethylene-alkyl (meth) acrylate copolymer. By using this polyolefin trunk, an excellent resistance to aging in light and at temperature is obtained.
  • the polyolefin trunk contains at least one unsaturated monomer residue (X) which can react on an acidic and / or amine function of the polyamide graft by a condensation reaction.
  • the unsaturated monomer (X) is not a "second comonomer”.
  • unsaturated monomer (X) included on the polyolefin trunk mention may be made of:
  • unsaturated epoxides are, for example, aliphatic glycidyl esters and ethers such as allyl glycidyl ether, vinyl glycidyl ether, glycidyl maleate and itaconate, acrylate and glycidyl methacrylate.
  • alicyclic glycidyl esters and ethers such as 2-cyclohexene-1-glycidyl ether, cyclohexene-4,5-diglycidylcarboxylate, cyclohexene-4-glycidyl carboxylate, 5-norbornene-2-methyl-2 glycidyl carboxylate and endocis-bicyclo (2,2,1) -5-heptene-2,3-diglycidyl dicarboxylate. It is preferred to use glycidyl methacrylate as the unsaturated epoxide.
  • Unsaturated carboxylic acids and their salts for example acrylic acid or methacrylic acid and the salts of these same acids.
  • carboxylic acid anhydrides may be chosen, for example, from maleic, itaconic, citraconic, allylsuccinic, cyclohex-4-ene-1,2-dicarboxylic, 4-methylenecyclohex-4-ene-1,2-dicarboxylic anhydrides, bicyclo (2,2,1) ) hept-5-ene-2,3-dicarboxylic acid, and x-methylbicyclo (2,2,1) hept-5-ene-2,2-dicarboxylic acid. It is preferred to use maleic anhydride as the carboxylic acid anhydride.
  • the unsaturated monomer (X) is preferably selected from unsaturated carboxylic acid anhydride and unsaturated epoxide.
  • the monomer unsaturated (X) is preferentially an unsaturated epoxide.
  • the unsaturated monomer (X) is advantageously an unsaturated epoxide and preferably an unsaturated carboxylic acid anhydride.
  • the preferred number of unsaturated monomer (X) attached on average to the polyolefin trunk is greater than or equal to 1, 3 and / or preferably less than or equal to 20.
  • (X) is maleic anhydride and the number molar mass of the polyolefin is 15,000 g / mol, it has been found that this corresponds to an anhydride proportion of at least 0.8% by weight of the entire polyolefin trunk and at most 6.5%.
  • the polyolefin trunk containing the remainder of the unsaturated monomer (X) is obtained by polymerization of the monomers (first comonomer, optional second comonomer, and optionally unsaturated monomer (X)). This polymerization can be carried out by a radical high-pressure process or a solution process, autoclave or tubular reactor, these processes and reactors being well known to those skilled in the art.
  • the unsaturated monomer (X) is not copolymerized in the polyolefin trunk, it is grafted onto the polyolefin trunk. Grafting is also an operation known per se.
  • the composition would be in accordance with the invention if several different functional monomers (X) were copolymerized and / or grafted on the polyolefin trunk.
  • the polyolefin trunk may be semicrystalline or amorphous.
  • amorphous polyolefins only the glass transition temperature is observed, whereas in the case of semi-crystalline polyolefins a glass transition temperature and a melting temperature (which will necessarily be higher) are observed. It will be sufficient for a person skilled in the art to select the monomer ratios and the molecular masses of the polyolefin trunk in order to easily obtain the desired values of glass transition temperature, possibly melting point and viscosity of the polyolefin trunk.
  • the polyolefin has a Melt Flow Index (MFI) of between 3 and 400 g / 10 min (190 ° C., 2.16 kg, ASTM D 1238).
  • MFI Melt Flow Index
  • the polyamide grafts are chosen here to have a glass transition temperature and melting temperature below 160 ° C.
  • cycloaliphatic homopolyamides which result from the condensation of a cycloaliphatic diamine and an aliphatic diacid.
  • a cycloaliphatic diamine mention may be made of 4,4'-methylenebis (cyclohexylamine), also known as para-bis (aminocyclohexyl) methane or PACM, 2,2'-dimethyl-4,4 Methylenebis (cyclohexylamine), also called bis- (3-methyl-4-aminocyclohexyl) -methane or BMACM.
  • polyamides PACM.12 resulting from the condensation of PACM with diacid in C12
  • BMACM.10 and BMACM.12 resulting from the condensation of BMACM with, respectively, aliphatic diacids. in C10 and C12. All these compounds are known to those skilled in the art.
  • the polyamide grafts coming into play in the composition according to the invention are preferably copolyamides. These result from the polycondensation of at least two of the groups of monomers stated above for obtaining homopolyamides.
  • the term "monomer” in the present description of copolyamides should be understood as “repetitive unit”. Indeed, the case where a repeating unit of the PA consists of the combination of a diacid with a diamine is particular. It is considered that it is the combination of a diamine and a diacid, that is to say the diamine-diacid couple (in equimolar quantity), which corresponds to the monomer. This is because individually, the diacid or diamine is only one structural unit, which is not enough by itself to polymerize to give a polyamide.
  • the copolyamides cover, in particular, the condensation products of: ⁇ at least two lactams,
  • At least two alpha, omega-aminocarboxylic aliphatic acids At least two alpha, omega-aminocarboxylic aliphatic acids
  • At least two diamines and at least two diacids At least one lactam with at least one diamine and at least one diacid,
  • At least one aliphatic alpha, omega-aminocarboxylic acid with at least one diamine and at least one diacid the diamine (s) and the diacid (s) possibly being independently of the other, aliphatic, cycloaliphatic or aromatic.
  • the copolyamides can be semi-crystalline or amorphous. In the case of amorphous copolyamides, only the glass transition temperature is observed, whereas in the case of semicrystalline copolyamides a glass transition temperature and a melting temperature (which will necessarily be higher) are observed.
  • copolyamides it is also possible to use semicrystalline copolyamides and particularly those of the PA 6/11, PA6 / 12 and PA6 / 11/12 type.
  • the degree of polymerization can vary widely, depending on whether it is a polyamide or a polyamide oligomer.
  • the polyamide grafts are mono-functional.
  • RI is hydrogen or a linear or branched alkyl group containing up to 20 carbon atoms
  • R2 is a group having up to 20 linear or branched alkyl or alkenyl carbon atoms, a saturated or unsaturated cycloaliphatic radical, an aromatic radical or a combination of the foregoing.
  • the limiter may be, for example, laurylamine or oleylamine.
  • R '1 -COOH For the polyamide graft to have a monocarboxylic acid terminus, it is sufficient to use a chain-limiting agent of the formula R '1 -COOH, R' 1 -CO-O-CO-R'2 or a dicarboxylic acid.
  • R 'I and R'2 are linear or branched alkyl groups containing up to 20 carbon atoms.
  • the polyamide graft has an amino functional end.
  • the preferred monofunctional polymerization limiters are laurylamine and oleylamine.
  • the polyamide grafts have a molar mass of between 1000 and 10000 g / mol. Since the stoichiometric ratio for the grafting of the polyamide grafts on the polyolefin trunk is constant, the choice of the mass of the polyamide grafts is a function of the mass of polyamide desired in the composition as explained above.
  • the condensation reaction of the polyamide graft on the polyolefin trunk containing the remainder of X is carried out by reaction of an amine or acid function of the polyamide graft on the remainder of X.
  • polyamide monoamine grafts are used and amide or imide bonds by reacting the amine function on the function of the remainder of X. This condensation is preferably carried out in the molten state.
  • compositions according to the invention To manufacture the composition according to the invention, conventional kneading and / or extrusion techniques can be used. The components of the composition are thus mixed to form a compound which may optionally be granulated at the die outlet.
  • coupling agents are added during compounding.
  • To obtain a nanostructured composition it is thus possible to mix the polyamide graft and the trunk in an extruder at a temperature generally of between 200 and 300 ° C.
  • the average residence time of the melt in the extruder can be between 5 seconds and 5 minutes, and preferably between 20 seconds and 1 minute.
  • the yield of this condensation reaction is evaluated by selective extraction of the free polyamide grafts, that is to say those which have not reacted to form the polyamide graft polymer.
  • the preparation of aminated end polyamide grafts and their addition to a polyolefin trunk containing the remainder of (X) is described in US3976720, US3963799, US5342886 and FR2291225.
  • the polyamide graft polymer of the present invention advantageously has a nanostructured organization.
  • the second polymer is a - the second polymer, present in the composition between 10% and 90% by weight, consists of a copolymer of ethylene and a non-reactive or non-functional comonomer of which the bending elastic modulus is less than 250 MPa at 23 ° C and has a crystalline melting point of between 60 ° C and 120 ° C.
  • this second polymer consists of a copolymer of ethylene and an alkyl (meth) acrylate.
  • this second polymer consists of a homopolymer of an olefin or a copolymer of at least one alphaolefin and at least one other copolymerizable monomer, provided of course that the conditions of modulus and crystalline melting point are met.
  • the flexible polyolefin is chosen from homo- or copolymeric polyethylenes.
  • alpha-olefins advantageously those having from 3 to 30 carbon atoms.
  • alpha-olefins having 3 to 30 carbon atoms as optional comonomers include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3 1-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, 1-dococene, 1-tetracocene, 1-hexacocene, 1-octacocene , and 1-triacontene.
  • These alpha-olefins can be used alone or in a mixture of two or more than two.
  • esters of unsaturated carboxylic acids such as, for example, alkyl (meth) acrylates, the alkyls having up to 24 carbon atoms.
  • alkyl acrylate or methacrylate examples include methyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate and 2-ethylhexyl acrylate.
  • vinyl esters of saturated carboxylic acids such as, for example, acetate or vinyl propionate.
  • dienes such as, for example, 1,4-hexadiene.
  • the flexible polyolefin may comprise several comonomers.
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • VLDPE very low density polyethylene
  • polyethylene obtained by metallocene catalysis that is to say polymers obtained by copolymerization of ethylene and alphaolefin such as propylene, butene, hexene or octene in the presence of a monosite catalyst generally consisting of a zirconium or titanium and two alkyl cyclic molecules bonded to the metal.
  • metallocene catalysts are usually composed of two metal-bound cyclopentadiene rings. These catalysts are frequently used with aluminoxanes as cocatalysts or activators, preferably methylaluminoxane (MAO). Hafnium may also be used as the metal to which cyclopentadiene is attached.
  • Other metallocenes may include transition metals of groups IV A, V A, and VI A. Metals of the lanthamide series may also be used.
  • EPDM elastomers (ethylene-propylene-diene)
  • ethylene-alkyl (meth) acrylate copolymers which may contain up to 60% by weight of (meth) acrylate and preferably 2 to 40%
  • ethylene such as copolymers obtained by high pressure radical formation of ethylene with vinyl acetate, (meth) acrylic acid esters (meth) ) and an alcohol having from 1 to 24 carbon atoms and preferably from 1 to 9, the radical terpolymers also using a third monomer chosen from unsaturated monomers copolymerizable with ethylene such as acrylic acid, maleic anhydride, glycidyl methacrylate.
  • These flexible copolymers can also be copolymers of ethylene with alfa-olefins of 3 to 8 carbon atoms, such as EPRs, ethylene very low density copolymers with butene of hexene or of octene with a density of between 0.870 and 0.910 g / cm 3 obtained by metallocene or Ziegler-Natta catalysis.
  • EPRs ethylene very low density copolymers with butene of hexene or of octene with a density of between 0.870 and 0.910 g / cm 3 obtained by metallocene or Ziegler-Natta catalysis.
  • flexible polyolefms we also mean mixtures of 2 or more flexible polyolefms.
  • the invention is particularly useful for copolymers of ethylene and alkyl (meth) acrylates.
  • the alkyl can have up to 24 carbon atoms.
  • the (meth) acrylates are chosen from those mentioned above.
  • These copolymers advantageously comprise up to 40% by weight of (meth) acrylate and preferably 3 to 35%.
  • Their MFI is advantageously between 0.1 and 50 (at 190 ° C. - 2.16 kg).
  • the flexural modulus is between 5 and 150 MPa.
  • the third optional polymer is a functionalized polyolefin comprising a copolymer of at least one alpha-olefin, such as ethylene or propylene, with at least one comonomer carrying a reactive function, chosen especially from a carboxylic acid, such as (meth) acrylic acid, a carboxylic anhydride, such as maleic anhydride, or an epoxide, such as glycidyl (meth) acrylate, and at least one other comonomer not carrying a reactive function, chosen for example from a different alpha-olefin; a diene such as butadiene; an unsaturated carboxylic acid ester, such as an alkyl (meth) acrylate wherein the alkyl group may be a methyl, ethyl or butyl group, especially; and a vinyl ester of carboxylic acid, such as vinyl acetate.
  • a carboxylic acid such as (meth) acrylic acid
  • Examples of unsaturated epoxides include:
  • aliphatic glycidyl esters and ethers such as allyl glycidyl ether, vinyl glycidyl ether, glycidyl maleate and itaconate, acrylate and glycidyl methacrylate, and
  • alicyclic glycidyl esters and ethers such as 2-cyclohexene-1-glycidyl ether, cyclohexene-4,5-diglycidylcarboxylate, cyclohexene-4-glycidyl carboxylate, 5-norbornene-2-methyl-2-glycidyl carboxylate and endocisbicyclo (2,2,1) -5-heptene-2,3-diglycidyl dicarboxylate.
  • unsaturated carboxylic acids their salts, their anhydrides.
  • unsaturated dicarboxylic acid anhydrides include maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride.
  • a copolymer comprising a reactive comonomer mention may be made of:
  • the ethylene (meth) acrylate-maleic anhydride copolymers obtained by copolymerization of the three monomers, the proportions of (meth) acrylate being as the above copolymers, the amount of maleic anhydride being up to 10% and of preferably 0.2 to 6% by weight.
  • the functionalized polyolefin contain from 60 to 100% by weight of alpha-olefin and from 0 to 40% by weight, preferably from 0 to 15% by weight, of comonomer not carrying a reactive function. It is further preferred that the functionalized polyolefin contain from 0.1 to 15% by weight, preferably from 0.5 to 5% by weight, of comonomer carrying a reactive function.
  • Examples of such polyolefins are functionalized ethylene / acrylic ester / glycidyl methacrylate and ethylene / acrylic ester / maleic anhydride, respectively available from Arkema under the trade name Lotader ® GMA and Lotader ® MAH.
  • compositions according to the invention may optionally be added to the composition according to the invention in order to confer on the latter such or such complementary functionality.
  • UV radiation Ultra Violet
  • UV stabilizers and UV absorbers such as benzotriazole, benzophenone and other hindered amines
  • UV stabilizers and UV absorbers such as benzotriazole, benzophenone and other hindered amines
  • UV stabilizers and UV absorbers can be added to ensure the transparency of the encapsulant during its lifetime.
  • These compounds may for example be based on benzophenone or benzotriazole.
  • We may be added in amounts less than 10% by weight of the total mass of the composition and preferably from 0.1 to 5%.
  • antioxidants to limit yellowing during the manufacture of the encapsulant such as phosphorus compounds (phosphonites and / or phosphites) and hindered phenolics. These antioxidants may be added in amounts of less than 10% by weight of the total mass of the composition and preferably from 0.1 to 5%.
  • Flame retardants may also be added. These agents may be halogenated or non-halogenated. Among the halogenated agents, mention may be made of brominated products. Phosphorus-based additives such as ammonium phosphate, polyphosphate phosphate, phosphinate or pyrophosphate phosphate, melamine cyanurate, pentaerythritol, zeolites and mixtures of these agents may also be used as non-halogenated agents.
  • the composition may comprise these agents in proportions ranging from 3 to 40% relative to the total mass of the composition.
  • pigments such as coloring or brightening compounds in proportions generally ranging from 5 to 15% relative to the total weight of the composition.
  • one skilled in the art can refer for example to the "Handbook of Photovoltaic Science and Engineering", Wiley, 2003 volume 7.
  • the grafting technique of polyamide grafts on the polyolefin trunk to obtain the polyamide graft polyolefin according to the invention is well known to those skilled in the art, and in particular the documents cited above FR 2912150, FR 2918150 or EP 21966489. It is not beyond the scope of the invention if crosslinking agents are added. Examples are isocyanates or organic peroxides. This crosslinking can also be carried out by known techniques of irradiation.
  • This crosslinking can be carried out by one of the many methods known to those skilled in the art, in particular by the use of thermally activated initiators, for example peroxide and azo compounds, photoinitiators such as benzophenone, by radiation comprising light rays, UV rays, electron beams and X-rays, silanes carrying reactive functional groups such as an amino silane, an epoxy silane, a vinyl silane such as, for example, vinyl silane tri-ethoxy or tri methoxy, and wet crosslinking.
  • thermally activated initiators for example peroxide and azo compounds
  • photoinitiators such as benzophenone
  • silanes carrying reactive functional groups such as an amino silane, an epoxy silane, a vinyl silane such as, for example, vinyl silane tri-ethoxy or tri methoxy
  • wet crosslinking wet crosslinking.
  • thermoplastic composition in a photovoltaic module
  • one skilled in the art can refer for example to the Handbook of Photo Voltaic Science and Engineering, Wiley, 2003.
  • the composition of the invention can be used as an encapsulant or encapsulant-backsheet in a photovoltaic module, the structure of which is described in relation to the appended figures.
  • Lotader 7500 terpolymer of ethylene, ethyl acrylate (17.5% by weight) and maleic anhydride (2.8% by weight) produced by ARKEMA having an MFI (190 ° C. under 2.16 kg) measured according to ISO 1133) of 70 g / 10 min (minute).
  • Lotader 5500 terpolymer of ethylene, ethyl acrylate (20% by weight) and maleic anhydride (2.8% by weight) produced by ARKEMA having an MFI (190 ° C. under 2.16 kg, measured according to ISO 1133) of 20 g / 10 min.
  • Lotryl 17 BA07 copolymer of ethylene and butyl acrylate (17% by weight) produced by ARKEMA having an MFI (190 ° C. under 2.16 kg measured according to ISO 1133) of 7 g / 10 min.
  • Lotryl 18MA02 copolymer of ethylene and methyl acrylate (18% by weight) produced by ARKEMA having an MFI (190 ° C. under 2.16 kg measured according to ISO 1133) of 2 g / 10 min.
  • Elvaloy AC 1820 copolymer of ethylene and methyl acrylate (20% by weight) produced by Dupont having an MFI (190 ° C. under 2.16 kg measured according to ISO 1133) of 8 g / 10 m
  • Prepolymer PA6 A PA6 prepolymer was synthesized by polycondensation from lactam 6. Laurylamine is used as a chain limiter so as to have a single primary amine functionality at the end of the chain. The number-average molar mass of the first prepolymer is 2500 g / mol.
  • Apolhya The Apolhya family is a family of polymers marketed by
  • ARKEMA which combines the properties of polyamides with those of polyolefins by obtaining co-continuous morphologies on a manometric scale.
  • Apolhya ® several types are selected:
  • Apolhya ⁇ D on the basis of Lotader ® 7500 and January 1 polyamide melting temperature of 190 ° C containing 20%> by weight of copolyamide.
  • Apolhya E on the basis of Lotader ® 7500 and 6/12 polyamide melting temperature of 130 ° C containing 50%> by weight of copolyamide.
  • Apolhya F on the basis of Lotader ® 5500 and 6/12 polyamide melting temperature of 130 ° C containing 20% by weight of copolyamide.
  • L / D 35
  • Monolayer films of 400 ⁇ (micrometer) were made by extrusion of flat film on a small laboratory extrusion line.
  • the compositions are obtained by mixing a polyamide grafted polyolefin, a copolymer of ethylene and an alkyl acrylate and optionally a third polyolefin functionalized with maleic anhydride. The proportions between the constituents are ensured by carrying out a dry bag mix of the granules prior to extrusion.
  • the extruder is a Haake 1 contra-rotating twin-screw equipped with a flat die 10 cm (cm) wide and 0.5 mm (mm) aperture.
  • the pipe elements are heated in a flat profile at 160 ° C for the illustrative examples of the invention based on copolyamide 6/12; the speed of rotation of the screws being 60 rpm (round per minute or "round per minute”).
  • the pipe elements are heated to a flat profile at 220 ° C., the speed of rotation of the screws being 60 rpm.
  • the pipe elements are heated to a flat profile at 180 ° C, the speed of rotation of the screws being 60 rpm.
  • the moisture recovery test consists in measuring the saturation humidity level obtained in a film of 400 ⁇ (micrometer) after conditioning done in moist heat at 85 ° C. and 85% relative humidity (RH). The humidity measurement is carried out according to the Karl-Fisher method based on the ISO 15512 standard. To measure the absorbed moisture content, the film is subjected to a thermal desorption step under nitrogen for 20 minutes at 200 ° C. .
  • composition domains for the composition according to the invention were established not only on the basis of this test in water recovery but also on thermomechanical properties tests such as a 100 ° C creep test, MFI ( "Melt Flow Index") as well as tests relating to optical properties (transparency test, yellowing in accelerated aging).
  • thermomechanical properties tests such as a 100 ° C creep test, MFI ( "Melt Flow Index") as well as tests relating to optical properties (transparency test, yellowing in accelerated aging).
  • compositions according to the invention namely the examples of compositions 1 to 10 exhibit excellent adhesive properties on glass, in particular after a wet heat aging test at 85 ° C. and 85% RH ( "Humidity Rate” or Humidity Rate).
  • Comparative Example 4 is unfit for application because the moisture recovery is too high and the melting temperature of the polyamide is unsuitable for the application.
  • the product does not flow at the usual manufacturing temperatures of the photovoltaic panels.
  • Comparative Example 5 is unfit for application because the melting temperature of the polyamide is unsuitable for the application. Indeed, the product does not flow at the usual manufacturing temperatures of photovoltaic panels.

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Abstract

The invention relates to a thermoplastic composition comprising a mixture of three particular and different polyolefins, including one consisting of a polyamide-grafted polyolefin having particular polyamide grafts (type and quantity). The invention also relates to a thermoplastic film and, more specifically, a film for encapsulating a photovoltaic module incorporating the polyamide-grafted polyolefin composition.

Description

COMPOSITION THERMOPLASTIQUE, NOTAMMENT POUR LES MODULES PHOTOVOLTAÏQUES  THERMOPLASTIC COMPOSITION, IN PARTICULAR FOR PHOTOVOLTAIC MODULES
Domaine de l'invention  Field of the invention
L'invention a pour objet une composition thermoplastique comprenant au moins une première polyoléfme particulière associée à une deuxième polyoléfme greffée polyamide dont les greffons présentent une température de transition vitreuse, ou de fusion, inférieure à 160°C. La présente invention concerne également l'utilisation de cette composition dans un module photovoltaïque, plus précisément dans une ou plusieurs des couches formant un tel module, plus particulièrement dans la couche formant encapsulant. The subject of the invention is a thermoplastic composition comprising at least a first particular polyolefin associated with a second polyamide grafted polyolefin whose grafts exhibit a glass transition temperature, or melting temperature, of less than 160 ° C. The present invention also relates to the use of this composition in a photovoltaic module, more precisely in one or more of the layers forming such a module, more particularly in the encapsulating layer.
Le réchauffement climatique, lié aux gaz à effet de serre dégagés par les énergies fossiles, a mené au développement de solutions énergétiques alternatives qui n'émettent pas de tels gaz lors de leur fonctionnement, comme par exemple les modules photo voltaïques. Un module photovoltaïque comprend une « pile photovoltaïque », cette pile étant capable de transformer l'énergie lumineuse en électricité.  Global warming, linked to greenhouse gas emissions from fossil fuels, has led to the development of alternative energy solutions that do not emit such gases during operation, such as photo voltaic modules. A photovoltaic module includes a "photovoltaic cell", this cell being capable of transforming light energy into electricity.
Il existe de nombreux types de structures de panneaux photovoltaïques.  There are many types of photovoltaic panel structures.
La structure d'un module photovoltaïque comprend classiquement trois couches, une couche centrale logeant les cellules photovoltaïques présentant des propriétés photoélectriques, entourée de part et d'autre d'une couche de protection.  The structure of a photovoltaic module conventionally comprises three layers, a central layer housing the photovoltaic cells having photoelectric properties, surrounded on both sides by a protective layer.
La couche centrale est dénommée classiquement encapsulant tandis que les couches de protection sont appelées « frontsheet », couche transparente destinée à autoriser le passage des rayons solaires, et « backsheet », couche devant être la plus étanche/hermétique possible.  The central layer is called classically encapsulating while the protective layers are called "frontsheet" transparent layer intended to allow the passage of solar rays, and "backsheet" layer to be the most waterproof / hermetic possible.
En présence de rayonnement solaire, il se crée un échauffement à l'intérieur du module solaire et des températures de 80°C (ou plus) peuvent être atteintes ce qui nécessite que les couches soient parfaitement liées les unes aux autres tout au long du cycle de vie du module.  In the presence of solar radiation, a heating inside the solar module is created and temperatures of 80 ° C (or more) can be reached which requires that the layers are perfectly connected to each other throughout the cycle. module life.
De manière générale, les modules photovoltaïques étant placés à l'extérieur et dans des environnements extrêmes, ils subissent des contraintes et des agressions constantes. Enfin, les propriétés des matériaux thermoplastiques utilisés doivent permettre de garantir une conservation à long terme des propriétés photoélectriques du module, autrement dit sans subir de dégradations notables. In general, photovoltaic modules being placed outside and in extreme environments, they undergo constant stress and aggression. Finally, the properties of the thermoplastic materials used must to guarantee a long-term preservation of the module's photoelectric properties, in other words without suffering any significant degradation.
Au titre des propriétés physico-chimique de ces matériaux thermoplastiques, on peut citer notamment une excellente tenue au fluage à 100°C ou plus, de bonnes propriétés optiques, de bonnes propriétés de durabilité en chaleur humide et sous UV (Ultra Violet), de bonnes propriétés électriques, une faible reprise en humidité et d'excellentes propriétés barrières.  The physico-chemical properties of these thermoplastic materials include, in particular, excellent creep resistance at 100 ° C. or higher, good optical properties, good durability properties in moist heat and under UV (Ultra Violet), good electrical properties, low moisture recovery and excellent barrier properties.
Etat de l'art State of the art
A l'heure actuelle, on connaît dans le domaine des modules photovoltaïques des compositions réticulables consistant en des polyoléfmes, en particulier de type EVA (Ethylène - Acétate de Vinyle), pour former l'encapsulant. Or, des problèmes de durabilité des modules photovoltaïques sont rencontrés avec ce type d'encapsulant notamment liés au relargage d'acide acétique en chaleur humide (85°C / 85 % HR : « Humidity Rate ») qui accélère la corrosion des cellules. Il est également connu que des modules photovoltaïques fabriqués avec ces copolymères éthylène - acétate de vinyle comme encapsulant sont particulièrement sensibles au problème de dégradation induite sous différence de potentiel mieux connu sous l'abréviation anglaise PID pour « Potential Induced Dégradation ». Il est également connu des encapsulants thermoplastiques de type polyoléfïne. Le problème de ces thermoplastiques est qu'ils ne tiennent pas en fluage, ce qui les rend impropres pour une telle application. At present, there are known in the field of photovoltaic modules crosslinkable compositions consisting of polyolefins, in particular of the EVA (Ethylene-Vinyl Acetate) type, to form the encapsulant. However, problems of durability of the photovoltaic modules are encountered with this type of encapsulant notably related to the release of acetic acid in wet heat (85 ° C / 85% RH: "Humidity Rate") which accelerates the corrosion of the cells. It is also known that photovoltaic modules manufactured with these ethylene-vinyl acetate copolymers as encapsulants are particularly sensitive to the problem of degradation induced under potential difference better known by the abbreviation PID for "Potential Induced Degradation". Thermoplastic encapsulants of the polyolefin type are also known. The problem with these thermoplastics is that they do not hold in creep, which makes them unfit for such an application.
On connaît par ailleurs une composition polyoléfïne greffée polyamide (greffons de polyamide fixés sur la chaîne principale). De telles compositions sont décrites dans les documents de la demanderesse FR 2918150 ou EP 2196489. Il a même déjà été envisagé de mélanger de telles polyoléfmes greffées polyamide avec une polyoléfïne, notamment dans le document WO 0228959 au nom de la demanderesse.  Furthermore, a polyolefin grafted polyamide composition (polyamide graft attached to the main chain) is known. Such compositions are described in the documents of the applicant FR 2918150 or EP 2196489. It has even already been envisaged to mix such polyamide graft polyolefins with a polyolefin, especially in WO 0228959 in the name of the applicant.
Néanmoins, de tels mélanges peuvent présenter un défaut majeur pour l'application photovoltaïque. En effet, ces mélanges engendrent un taux d'humidité élevé (reprise d'eau importante) ce qui limite la durabilité des modules photovoltaïques (chute du rendement) après un certain temps d'utilisation ou lors de tests en chaleur humides sous polarisation. Brève description de l'invention Nevertheless, such mixtures can present a major defect for the photovoltaic application. Indeed, these mixtures generate a high humidity (significant water uptake) which limits the durability of photovoltaic modules (yield drop) after a certain time of use or during wet heat tests under polarization. Brief description of the invention
Il a été constaté par la demanderesse, après diverses expériences et manipulations, que, contrairement aux enseignements bien connus de l'homme du métier, un choix particulier de greffons polyamide (pour la polyoléfïne greffée polyamide), présents en poids de la composition dans un taux bien spécifique, combiné à celui de deux polyoléfïnes spécifiques, dans des taux appropriés, permet de résoudre les problèmes liés aux compositions de l'art antérieur, en particulier celle divulguée dans le document WO 0228959. It has been found by the Applicant, after various experiments and manipulations, that, contrary to the teachings well known to those skilled in the art, a particular choice of polyamide graft (for polyolefin grafted polyamide), present by weight of the composition in a A very specific rate, combined with that of two specific polyolefins, at appropriate levels, makes it possible to solve the problems related to the compositions of the prior art, in particular that disclosed in the document WO 0228959.
Ainsi, la composition selon la présente invention, tout en conservant des propriétés mécanique, thermomécanique, optique, électrique, tout à fait satisfaisantes, comble les dernières lacunes que peuvent présenter ces matériaux thermoplastiques par ailleurs extrêmement performants, à savoir que cette composition présente une reprise à l'eau faible, voire très faible, et une dégradation dans le temps (chute de résistivité électrique) particulièrement améliorée.  Thus, the composition according to the present invention, while retaining mechanical, thermomechanical, optical, electrical, quite satisfactory properties, fills the last deficiencies that can present these thermoplastic materials otherwise extremely powerful, namely that this composition has a recovery. at low water, or very low, and degradation over time (electrical resistivity drop) particularly improved.
Ainsi, la présente invention concerne une composition thermoplastique comprenant au moins un mélange de trois polymères, dans laquelle : Thus, the present invention relates to a thermoplastic composition comprising at least one mixture of three polymers, wherein:
- le premier polymère, présent dans la composition entre 10% et 70% en poids, consiste en un polymère greffé polyamide présentant un tronc en polyoléfïne contenant un reste d'au moins un monomère insaturé (X) et une pluralité de greffons en polyamide, dans lequel :  the first polymer, present in the composition between 10% and 70% by weight, consists of a polyamide graft polymer having a polyolefin trunk containing a residue of at least one unsaturated monomer (X) and a plurality of polyamide grafts, in which :
- les greffons en polyamide sont attachés au tronc en polyoléfïne par le reste du monomère insaturé (X) comprenant une fonction capable de réagir par une réaction de condensation avec un polyamide ayant au moins une extrémité aminé et/ou au moins une extrémité acide carboxylique,  the polyamide grafts are attached to the polyolefin trunk by the remainder of the unsaturated monomer (X) comprising a function capable of reacting by a condensation reaction with a polyamide having at least one amine end and / or at least one carboxylic acid end,
- le reste du monomère insaturé (X) est fixé sur le tronc par greffage ou copolymérisation,  the rest of the unsaturated monomer (X) is attached to the trunk by grafting or copolymerization,
- les greffons en polyamide représentent de 10%> à 60%>, de préférence de 15% à 55%), en poids dudit polymère greffé polyamide,  the polyamide grafts represent from 10% to 60%, preferably from 15% to 55%, by weight of said polyamide graft polymer,
- le second polymère, présent dans la composition entre 10 % et 90 % en poids, consiste en un copolymère d'éthylène et d'un comonomère non réactif ou non fonctionnalisé dont le module élastique en flexion est inférieur à 250 Mpa à 23°C et qui présente un point de fusion cristalline compris entre 60°C et 120°C, the second polymer, present in the composition between 10% and 90% by weight, consists of a copolymer of ethylene and a non-reactive or non-functional comonomer whose flexural modulus of elasticity is less than 250 MPa at 23 ° C and has a crystalline melting point of between 60 ° C and 120 ° C,
- le troisième polymère, présent dans la composition entre 3 % et 45 % en poids de ladite composition, consistant en une polyoléfme fonctionnalisée comprenant un copolymère d'au moins une alpha-oléfïne, telle que l'éthylène ou le propylène, avec au moins un comonomère portant une fonction réactive, et au moins un autre comonomère ne portant pas de fonction réactive, choisi parmi une alpha-oléfïne différente de la susdite alpha-oléfïne, un diène, un ester d'acide carboxylique insaturé, et un ester vinylique d'acide carboxylique, un anhydride d'acide dicarboxylique comme Γ anhydride maléique,  the third polymer, present in the composition, between 3% and 45% by weight of said composition, consisting of a functionalized polyolefin comprising a copolymer of at least one alpha-olefin, such as ethylene or propylene, with at least a comonomer bearing a reactive function, and at least one other comonomer not carrying a reactive function, chosen from an alpha-olefin different from the aforesaid alpha-olefin, a diene, an unsaturated carboxylic acid ester, and a vinyl ester, carboxylic acid, a dicarboxylic acid anhydride such as maleic anhydride,
caractérisée en ce que les greffons en polyamide du susdit premier polymère présentent une température de transition vitreuse ainsi qu'une température de fusion inférieures ou égale à 160°C,  characterized in that the polyamide grafts of the above-mentioned first polymer have a glass transition temperature and a melting temperature of less than or equal to 160 ° C,
et en ce que le taux des greffons polyamide dudit premier polymère représente de 3 % à 15 %, de préférence entre 5 % et 12,5 %, en poids de la composition thermoplastique.  and in that the level of the polyamide grafts of said first polymer is from 3% to 15%, preferably from 5% to 12.5%, by weight of the thermoplastic composition.
Selon une possibilité offerte par l'invention, le second polymère consistera en un copolymère de l'éthylène et d'un (méth)acrylate d'alkyle. According to a possibility offered by the invention, the second polymer will consist of a copolymer of ethylene and an alkyl (meth) acrylate.
De préférence, le troisième polymère consiste en un copolymère éthylène - ester acrylique - méthacrylate de glycidyle ou éthylène - ester acrylique - anhydride maléique. Preferably, the third polymer is an ethylene - acrylic ester - glycidyl methacrylate or ethylene - acrylic ester - maleic anhydride copolymer.
Avantageusement, le troisième polymère est présent entre 10% et 30%>, en poids de la composition.  Advantageously, the third polymer is present between 10% and 30% by weight of the composition.
D'autres caractéristiques avantageuses de l'invention sont précisées dans la suite : Avantageusement, la masse molaire en nombre des susdits greffons polyamide du susdit polymère greffé est comprise dans la gamme allant de 1000 à 10000 g/mol. Other advantageous features of the invention are specified below: Advantageously, the molar mass in number of the aforesaid polyamide grafts of the aforesaid graft polymer is in the range of 1000 to 10000 g / mol.
Selon une particularité de l'invention, pour les susdits polymères greffés, le nombre de monomère (X) fixé sur le tronc en polyoléfme est supérieur ou égal à 1,3 et/ou inférieur ou égal à 20. Selon un aspect de l'invention, le susdit premier polymère est présent entre 10% et 50% en poids de la composition. According to one particularity of the invention, for the aforesaid graft polymers, the number of monomer (X) attached to the polyolefin trunk is greater than or equal to 1.3 and / or less than or equal to 20. According to one aspect of the invention, the aforesaid first polymer is present between 10% and 50% by weight of the composition.
De préférence, les greffons polyamide du première polymère consistent en des copolyamides choisi parmi les copolyamides PA 6/11, PA6/12 et PA6/11/12.  Preferably, the polyamide grafts of the first polymer consist of copolyamides chosen from copolyamides PA 6/11, PA6 / 12 and PA6 / 11/12.
De préférence, le monomère insaturé (X) du premier polymère est un anhydride maléique.  Preferably, the unsaturated monomer (X) of the first polymer is a maleic anhydride.
De préférence, le second polymère est présent dans la composition entre dans la composition entre 40%> et 70%> en poids.  Preferably, the second polymer present in the composition is between 40% and 70% by weight.
Selon une possibilité offerte par l'invention, la composition selon l'invention consiste uniquement en les trois susdits polymères.  According to a possibility offered by the invention, the composition according to the invention consists solely of the three aforesaid polymers.
L'invention se rapporte également à un film comprenant la composition selon l'invention telle que décrite ci-dessus. The invention also relates to a film comprising the composition according to the invention as described above.
L'invention concerne également un film thermoplastique d'un module photovoltaïque, ledit module photovoltaïque comprenant au moins deux couches dont l'une forme la couche d'encapsulant, caractérisé en ce que la couche d'encapsulant comprend, de préférence consiste en, la composition thermoplastique telle que décrite précédemment.  The invention also relates to a thermoplastic film of a photovoltaic module, said photovoltaic module comprising at least two layers, one of which forms the encapsulating layer, characterized in that the encapsulant layer comprises, preferably consists of, the thermoplastic composition as described above.
De préférence, la couche formant encapsulant comprend des promoteurs d'adhésion consistant en un ingrédient non polymérique, de nature organique, cristalline ou minéral et plus préférentiellement semi-minéral semi-organique des antioxydants et/ou des agents anti-UVs.  Preferably, the encapsulant layer comprises adhesion promoters consisting of a non-polymeric, organic, crystalline or inorganic ingredient and more preferably semi-inorganic semi-organic antioxidants and / or anti-UV agents.
Il doit être noté que la composition selon l'invention est présentée avec pour application un module photovoltaïque, plus particulièrement sa couche d'encapsulant, mais bien entendu cette composition pourra être envisagée pour toutes autres applications où une telle composition est avantageusement utilisable, notamment dans les structures multicouches telles que par exemple des chaussures, les films ou revêtements adhésifs, ou les tubes de transport de fluides. La description qui va suivre est donnée uniquement à titre illustratif et non limitatif. Description détaillée de l'invention It should be noted that the composition according to the invention is presented with for application a photovoltaic module, more particularly its encapsulant layer, but of course this composition may be envisaged for all other applications where such a composition is advantageously usable, especially in multilayer structures such as, for example, shoes, adhesive films or coatings, or fluid transport tubes. The following description is given solely for illustrative and not limiting. Detailed description of the invention
S'agissant du premier polymère susmentionné, il s'agit donc d'un polymère greffé, avec entre 10% et 70%>, de préférence entre 15% et 55%, en masse de greffons polyamide et un nombre de monomères (X) compris entre 1,3 et 20.  As regards the first polymer mentioned above, it is therefore a graft polymer, with between 10% and 70%>, preferably between 15% and 55%, by mass of polyamide grafts and a number of monomers (X) between 1.3 and 20.
S'agissant du tronc polyoléfme, c'est un polymère comprenant comme monomère une a-oléfîne.  As regards the polyolefin trunk, it is a polymer comprising as monomer an α-olefin.
On préfère les a-oléfmes ayant de 2 à 30 atomes de carbone. Α-olefins having 2 to 30 carbon atoms are preferred.
A titre d'a-oléfme, on peut citer l'éthylène, le propylène, 1 -butène, 1-pentène, 3- méthyl-1 -butène, 1-hexène, 4-méthyl- 1-pentène, 3-méthyl- 1-pentène, 1-octène, 1- décène, 1-dodécène, 1-tétradécène, 1-hexadécène, 1-octadécène, 1-eicocène, 1- dococène, 1-tétracocène, 1-hexacocène, 1-octacocène, et 1-triacontène. As α-olefin, mention may be made of ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl- 1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, 1-dococene, 1-tetracocene, 1-hexacocene, 1-octacocene, and 1-octene -triacontène.
On peut également citer les cyclo-oléfînes ayant de 3 à 30 atomes de carbone, préférentiellement de 3 à 20 atomes de carbone, tels que le cyclopentane, le cycloheptène, le norbornène, le 5-méthyl-2-norbomène, le tétracyclododécène, et le 2- méthyl-l,4,5,8-diméthano-l,2,3,4,4a,5,8,8a-octahydronaphthalène ; di et polyoléfines, telles que la butadiène, l'isoprène, le 4-méthyl- 1,3-pentadiène, le 1 ,4-pentadiène, 1,5- hexadiène, 1,3-hexadiène, 1,3 -octadiène, 1,4-octadiène, 1,5-octadiène, 1,6-octadiène, l'éthylidènenorbomène, le vinyle norbornène, le dicyclopentadiène, le 7-méthyl-l,6- octadiène, le 4-éthylidiène-8-méthyl-l,7-nonadiène, et le 5,9-diméthyl-l,4,8-décatriène ; les composés vinyliques aromatiques tels que le mono- ou poly alkylstyrènes (comprenant le styrène, o-méthylstyrène, m-méthylstyrène, p-méthylstyrène, o,p- diméthylstyrène, o-éthylstyrène, m-éthylstyrène et p-éthylstyrène), et les dérivés comprenant des groupes fonctionnels tels que le méthoxystyrène, l'éthoxy styrène, l'acide benzoïque vinylique, le benzoate de méthyle vinyle, l'acétate de benzyle vinyle, l'hydroxystyrène, Γο-chlorostyrène, le p-chlorostyrène, le di-vinyle benzène, le 3- phénylpropène, le 4-phénylpropène, le α-méthylstyrène, le vinyle chloride, le 1,2- difluoroéthylène, le 1 ,2-dichloroéthylène, le tétrafluoroéthylène, et le 3,3,3 -trifluoro-1- propène. Mention may also be made of cycloolefins having from 3 to 30 carbon atoms, preferably from 3 to 20 carbon atoms, such as cyclopentane, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene; di and polyolefins, such as butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1 , 4-octadiene, 1,5-octadiene, 1,6-octadiene, ethylidenenorbornene, vinyl norbornene, dicyclopentadiene, 7-methyl-1,6-octadiene, 4-ethylidiene-8-methyl-1, 7-nonadiene, and 5,9-dimethyl-1,4,8-decatriene; vinyl aromatic compounds such as mono- or polyalkylstyrenes (including styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene and p-ethylstyrene), and derivatives comprising functional groups such as methoxystyrene, ethoxy styrene, vinyl benzoic acid, methyl vinyl benzoate, benzyl vinyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, vinyl benzene, 3-phenylpropene, 4-phenylpropene, α-methylstyrene, vinyl chloride, 1,2-difluoroethylene, 1,2-dichloroethylene, tetrafluoroethylene, and 3,3,3-trifluoro-1 - propene.
Dans le cadre de la présente invention, le terme d'a-oléfme comprend également le styrène. On préfère le propylène et tout spécialement l'éthylène comme a-oléfîne. Cette polyoléfïne peut-être un homopolymère lorsqu'une seule a-oléfine est polymérisée dans la chaîne polymère. On peut citer comme exemples le polyéthylène (PE) ou le polypropylène (PP). In the context of the present invention, the term α-olefin also includes styrene. Propylene and especially ethylene are preferred as α-olefins. This polyolefin may be a homopolymer when a single α-olefin is polymerized in the polymer chain. Examples include polyethylene (PE) or polypropylene (PP).
Cette polyoléfïne peut aussi être un copolymère lorsqu'au moins deux comonomères sont copolymérisés dans la chaîne polymère, l'un des deux comonomères dit le « premier comonomère » étant une α-oléfïne et l'autre comonomère, dit « deuxième comonomère », est un monomère capable de polymériser avec le premier monomère. This polyolefin can also be a copolymer when at least two comonomers are copolymerized in the polymer chain, one of the two comonomers said the "first comonomer" being an α-olefin and the other comonomer, called "second comonomer", is a monomer capable of polymerizing with the first monomer.
A titre de deuxième comonomère, on peut citer : · une des α-oléfïnes déjà citées, celle-ci étant différente du premier comonomère a-oléfine, As a second comonomer, mention may be made of: one of the α-olefins already mentioned, this being different from the first α-olefin comonomer,
• les diènes tels que par exemple le 1,4-hexadiène, l'éthylidène norbornène, le butadiène Dienes such as for example 1,4-hexadiene, ethylidene norbornene, butadiene
• les esters d'acides carboxyliques insaturés tels que par exemple les acrylates d'alkyle ou les méthacrylates d'alkyle regroupés sous le terme (méth)acrylates d'alkyles. Les chaînes alkyles de ces (méth)acrylates peuvent avoir jusqu'à 30 atomes de carbone. On peut citer comme chaînes alkyles le méthyle, l'éthyle, le propyl, n-butyl, sec-butyl, Isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2- ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, hencosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl. On préfère les (méth)acrylates de méthyle, éthyle et butyle comme esters d'acide carboxylique insaturés. Unsaturated carboxylic acid esters such as, for example, alkyl acrylates or alkyl methacrylates grouped under the term alkyl (meth) acrylates. The alkyl chains of these (meth) acrylates can have up to 30 carbon atoms. Mention may be made, as alkyl chains, of methyl, ethyl, propyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl and dodecyl. tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, hencosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl. Methyl, ethyl and butyl (meth) acrylates are preferred as unsaturated carboxylic acid esters.
• les esters vinyliques d'acide carboxyliques. A titre d'exemples d'esters vinyliques d'acide carboxylique, on peut citer l'acétate de vinyle, le versatate de vinyle, le propionate de vinyle, le butyrate de vinyle, ou le maléate de vinyle. On préfère l'acétate de vinyle comme ester vinylique d'acide carboxylique. • vinyl esters of carboxylic acid. As examples of vinyl esters of carboxylic acid, mention may be made of vinyl acetate, vinyl versatate, vinyl propionate, vinyl butyrate, or vinyl maleate. Vinyl acetate is preferred as the carboxylic acid vinyl ester.
Avantageusement, le tronc en polyoléfïne comprend au moins 50 % en moles du premier comonomère ; sa densité peut être avantageusement comprise entre 0,91 et 0,96. Les troncs polyoléfmes préférés sont constitués d'un copolymère éthylène- (méth)acrylate d'alkyle. En utilisant ce tronc polyoléfine, on obtient une excellente tenue au vieillissement à la lumière et à la température. Advantageously, the polyolefin trunk comprises at least 50 mol% of the first comonomer; its density may advantageously be between 0.91 and 0.96. The preferred polyolefin trunks consist of an ethylene-alkyl (meth) acrylate copolymer. By using this polyolefin trunk, an excellent resistance to aging in light and at temperature is obtained.
On ne sortirait pas du cadre de l'invention si différents « deuxièmes comonomères » étaient copolymérisés dans le tronc polyoléfine. It would not be departing from the scope of the invention if different "second comonomers" were copolymerized in the polyolefin trunk.
Selon la présente invention, le tronc polyoléfine contient au moins un reste de monomère insaturé (X) pouvant réagir sur une fonction acide et/ou aminé du greffon polyamide par une réaction de condensation. Selon la définition de l'invention, le monomère insaturé (X) n'est pas un « deuxième comonomère ». Comme monomère insaturé (X) compris sur le tronc polyoléfine, on peut citer : According to the present invention, the polyolefin trunk contains at least one unsaturated monomer residue (X) which can react on an acidic and / or amine function of the polyamide graft by a condensation reaction. According to the definition of the invention, the unsaturated monomer (X) is not a "second comonomer". As unsaturated monomer (X) included on the polyolefin trunk, mention may be made of:
• les époxydes insaturés. Parmi ceux-ci, ce sont par exemple les esters et éthers de glycidyle aliphatiques tels que l'allylglycidyléther, le vinylglycidyléther, le maléate et l'itaconate de glycidyle, l'acrylate et le méthacrylate de glycidyle. Ce sont aussi par exemple les esters et éthers de glycidyle alicycliques tels que le 2- cyclohexène-l-glycidyléther, le cyclohexène-4,5-diglycidylcarboxylate, le cyclohexène-4-glycidyl carboxylate, le 5-norbornène-2-méthyl-2-glycidyl carboxylate et l'endocis-bicyclo(2,2,l)-5-heptène-2,3-diglycidyl dicarboxylate. On préfère utiliser le méthacrylate de glycidyle comme époxyde insaturé. • unsaturated epoxides. Among these are, for example, aliphatic glycidyl esters and ethers such as allyl glycidyl ether, vinyl glycidyl ether, glycidyl maleate and itaconate, acrylate and glycidyl methacrylate. They are also, for example, alicyclic glycidyl esters and ethers such as 2-cyclohexene-1-glycidyl ether, cyclohexene-4,5-diglycidylcarboxylate, cyclohexene-4-glycidyl carboxylate, 5-norbornene-2-methyl-2 glycidyl carboxylate and endocis-bicyclo (2,2,1) -5-heptene-2,3-diglycidyl dicarboxylate. It is preferred to use glycidyl methacrylate as the unsaturated epoxide.
• les acides carboxyliques insaturés et leurs sels, par exemple l'acide acrylique ou l'acide méthacrylique et les sels de ces mêmes acides. Unsaturated carboxylic acids and their salts, for example acrylic acid or methacrylic acid and the salts of these same acids.
• les anhydrides d'acide carboxylique. Ils peuvent être choisis par exemple parmi les anhydrides maléique, itaconique, citraconique, allylsuccinique, cyclohex-4- ène- 1 ,2-dicarboxylique, 4-méthylènecyclohex-4-ène- 1 ,2-dicarboxylique, bicyclo(2,2,l)hept-5-ène-2,3-dicarboxylique, et x-méthylbicyclo(2,2,l)hept-5- ène-2,2-dicarboxylique. On préfère utiliser l'anhydride maléique comme anhydride d'acide carboxylique. • carboxylic acid anhydrides. They may be chosen, for example, from maleic, itaconic, citraconic, allylsuccinic, cyclohex-4-ene-1,2-dicarboxylic, 4-methylenecyclohex-4-ene-1,2-dicarboxylic anhydrides, bicyclo (2,2,1) ) hept-5-ene-2,3-dicarboxylic acid, and x-methylbicyclo (2,2,1) hept-5-ene-2,2-dicarboxylic acid. It is preferred to use maleic anhydride as the carboxylic acid anhydride.
Le monomère insaturé (X) est de préférence choisi parmi un anhydride d'acide carboxylique insaturé et un époxyde insaturé. En particulier, pour réaliser la condensation du greffon polyamide avec le tronc polyoléfine, dans le cas où l'extrémité réactive du greffon en polyamide est une fonction acide carboxylique, le monomère insaturé (X) est préférentiellement un époxyde insaturé. Dans le cas où l'extrémité réactive du greffon en polyamide est une fonction aminé, le monomère insaturé (X) est avantageusement un époxyde insaturé et préférentiellement un anhydride d'acide carboxylique insaturé. Selon une version avantageuse de l'invention, le nombre préféré de monomère insaturé (X) fixé en moyenne sur le tronc polyoléfïne est supérieur ou égal à 1 ,3 et/ou préférentiellement inférieur ou égal à 20. The unsaturated monomer (X) is preferably selected from unsaturated carboxylic acid anhydride and unsaturated epoxide. In particular, to carry out the condensation of the polyamide graft with the polyolefin trunk, in the case where the reactive end of the polyamide graft is a carboxylic acid function, the monomer unsaturated (X) is preferentially an unsaturated epoxide. In the case where the reactive end of the polyamide graft is an amine function, the unsaturated monomer (X) is advantageously an unsaturated epoxide and preferably an unsaturated carboxylic acid anhydride. According to an advantageous version of the invention, the preferred number of unsaturated monomer (X) attached on average to the polyolefin trunk is greater than or equal to 1, 3 and / or preferably less than or equal to 20.
Ainsi, si (X) est l'anhydride maléique et la masse molaire en nombre de la polyoléfïne est 15 000 g/mol, on a trouvé que ceci correspondait à une proportion d'anhydride d'au moins 0,8 % en masse de l'ensemble du tronc de polyoléfïne et d'au plus 6,5%. Ces valeurs associées à la masse des greffons polyamide déterminent la proportion de polyamide et de tronc dans le polymère greffé polyamide. Thus, if (X) is maleic anhydride and the number molar mass of the polyolefin is 15,000 g / mol, it has been found that this corresponds to an anhydride proportion of at least 0.8% by weight of the entire polyolefin trunk and at most 6.5%. These values associated with the mass of the polyamide grafts determine the proportion of polyamide and trunk in the polyamide graft polymer.
Le tronc polyoléfïne contenant le reste du monomère insaturé (X) est obtenu par polymérisation des monomères (premier comonomère, deuxième comonomère éventuel, et éventuellement monomère insaturé (X)). On peut réaliser cette polymérisation par un procédé radicalaire à haute pression ou un procédé en solution, en réacteur autoclave ou tubulaire, ces procédés et réacteurs étant bien connus de l'homme du métier. Lorsque le monomère insaturé (X) n'est pas copolymérisé dans le tronc polyoléfïne, il est greffé sur le tronc polyoléfïne. Le greffage est également une opération connue en soi. La composition serait conforme à l'invention si plusieurs monomères fonctionnels (X) différents étaient copolymérisés et/ou greffés sur le tronc polyoléfïne. The polyolefin trunk containing the remainder of the unsaturated monomer (X) is obtained by polymerization of the monomers (first comonomer, optional second comonomer, and optionally unsaturated monomer (X)). This polymerization can be carried out by a radical high-pressure process or a solution process, autoclave or tubular reactor, these processes and reactors being well known to those skilled in the art. When the unsaturated monomer (X) is not copolymerized in the polyolefin trunk, it is grafted onto the polyolefin trunk. Grafting is also an operation known per se. The composition would be in accordance with the invention if several different functional monomers (X) were copolymerized and / or grafted on the polyolefin trunk.
Selon les types et ratio de monomères, le tronc polyoléfïne peut être semi- cristallin ou amorphe. Dans le cas des polyoléfïnes amorphes, seule la température de transition vitreuse est observée, tandis que dans celui des polyoléfïnes semi-cristallins une température de transition vitreuse et une température de fusion (qui sera nécessairement supérieure) sont observées. Il suffira à l'homme du métier de sélectionner les ratios de monomère et les masses moléculaires du tronc polyoléfïne pour pouvoir obtenir aisément les valeurs voulues de température de transition vitreuse, éventuellement de température de fusion ainsi que de viscosité du tronc polyoléfïne. De manière préférée, la polyoléfïne a un Melt Flow Index (MFI) compris entre 3 et 400g/10min (190°C, 2,16kg, ASTM D 1238). Les greffons polyamides sont ici choisis pour présenter une température de transition vitreuse et de fusion inférieure à 160°C. Depending on the types and ratio of monomers, the polyolefin trunk may be semicrystalline or amorphous. In the case of amorphous polyolefins, only the glass transition temperature is observed, whereas in the case of semi-crystalline polyolefins a glass transition temperature and a melting temperature (which will necessarily be higher) are observed. It will be sufficient for a person skilled in the art to select the monomer ratios and the molecular masses of the polyolefin trunk in order to easily obtain the desired values of glass transition temperature, possibly melting point and viscosity of the polyolefin trunk. Preferably, the polyolefin has a Melt Flow Index (MFI) of between 3 and 400 g / 10 min (190 ° C., 2.16 kg, ASTM D 1238). The polyamide grafts are chosen here to have a glass transition temperature and melting temperature below 160 ° C.
On peut notamment citer les homopolyamides cycloaliphatiques qui résultent de la condensation d'une diamine cycloaliphatique et d'un diacide aliphatique. A titre d'exemple de diamine cycloaliphatique, on peut citer la 4,4'-méthylene- bis(cyclohexylamine), encore dénommée para-bis(aminocyclo-hexyl)méthane ou PACM, la 2,2'-diméthyl-4,4'méthylène-bis(cyclo-hexyl-amine), encore dénommée bis- (3-méthyl-4-aminocyclohexyl)-méthane ou BMACM. Mention may in particular be made of cycloaliphatic homopolyamides which result from the condensation of a cycloaliphatic diamine and an aliphatic diacid. As an example of a cycloaliphatic diamine, mention may be made of 4,4'-methylenebis (cyclohexylamine), also known as para-bis (aminocyclohexyl) methane or PACM, 2,2'-dimethyl-4,4 Methylenebis (cyclohexylamine), also called bis- (3-methyl-4-aminocyclohexyl) -methane or BMACM.
Ainsi, parmi les homopolyamides cycloaliphatiques, on peut citer les polyamides PACM.12, résultant de la condensation du PACM avec le diacide en C12, les BMACM.10 et BMACM.12 résultant de la condensation de la BMACM avec, respectivement, les diacides aliphatiques en C10 et en C12. Tous ces composés sont connus de l'homme du métier. Thus, among the cycloaliphatic homopolyamides, mention may be made of polyamides PACM.12, resulting from the condensation of PACM with diacid in C12, BMACM.10 and BMACM.12 resulting from the condensation of BMACM with, respectively, aliphatic diacids. in C10 and C12. All these compounds are known to those skilled in the art.
Les greffons polyamide rentrant en jeu dans la composition selon l'invention sont préférentiellement des copolyamides. Ceux-ci résultent de la polycondensation d'au moins deux des groupes de monomères énoncés ci-dessus pour l'obtention d'homopolyamides. Le terme « monomère » dans la présente description des copolyamides doit être pris au sens d' « unité répétitive ». En effet, le cas où une unité répétitive du PA est constituée de l'association d'un diacide avec une diamine est particulier. On considère que c'est l'association d'une diamine et d'un diacide, c'est-à- dire le couple diamine-diacide (en quantité équimolaire), qui correspond au monomère. Ceci s'explique par le fait qu'individuellement, le diacide ou la diamine n'est qu'une unité structurale, qui ne suffit pas à elle seule à polymériser pour donner un polyamide. The polyamide grafts coming into play in the composition according to the invention are preferably copolyamides. These result from the polycondensation of at least two of the groups of monomers stated above for obtaining homopolyamides. The term "monomer" in the present description of copolyamides should be understood as "repetitive unit". Indeed, the case where a repeating unit of the PA consists of the combination of a diacid with a diamine is particular. It is considered that it is the combination of a diamine and a diacid, that is to say the diamine-diacid couple (in equimolar quantity), which corresponds to the monomer. This is because individually, the diacid or diamine is only one structural unit, which is not enough by itself to polymerize to give a polyamide.
Ainsi, les copolyamides couvrent notamment les produits de condensation : · d'au moins deux lactames, Thus, the copolyamides cover, in particular, the condensation products of: · at least two lactams,
• d'au moins deux acides alpha, omega-aminocarboxyliques aliphatiques, At least two alpha, omega-aminocarboxylic aliphatic acids,
• d'au moins un lactame et d'au moins un acide alpha, omega-aminocarboxylique aliphatique, At least one lactam and at least one aliphatic alpha, omega-aminocarboxylic acid,
• d'au moins deux diamines et d'au moins deux diacides, • d'au moins un lactame avec au moins une diamine et au moins un diacide, At least two diamines and at least two diacids, At least one lactam with at least one diamine and at least one diacid,
• d'au moins un acide alpha,omega-aminocarboxylique aliphatique avec au moins une diamine et au moins un diacide, la(les) diamine(s) et le(s) diacide(s) pouvant être, indépendamment l'un de l'autre, aliphatiques, cycloaliphatiques ou aromatiques. At least one aliphatic alpha, omega-aminocarboxylic acid with at least one diamine and at least one diacid, the diamine (s) and the diacid (s) possibly being independently of the other, aliphatic, cycloaliphatic or aromatic.
Selon les types et ratio de monomères, les copolyamides peuvent être semi- cristallins ou amorphes. Dans le cas des copolyamides amorphes, seule la température de transition vitreuse est observée, tandis que dans celui des copolyamides semi- cristallins une température de transition vitreuse et une température de fusion (qui sera nécessairement supérieure) sont observées. Depending on the types and ratio of monomers, the copolyamides can be semi-crystalline or amorphous. In the case of amorphous copolyamides, only the glass transition temperature is observed, whereas in the case of semicrystalline copolyamides a glass transition temperature and a melting temperature (which will necessarily be higher) are observed.
Parmi les copolyamides, on pourra également utiliser les copolyamides semi- cristallins et particulièrement ceux de type PA 6/11, PA6/12 et PA6/11/12. Among the copolyamides, it is also possible to use semicrystalline copolyamides and particularly those of the PA 6/11, PA6 / 12 and PA6 / 11/12 type.
Le degré de polymérisation peut varier dans de larges proportions, selon sa valeur c'est un polyamide ou un oligomère de polyamide. Avantageusement, les greffons polyamide sont mono fonctionnels. The degree of polymerization can vary widely, depending on whether it is a polyamide or a polyamide oligomer. Advantageously, the polyamide grafts are mono-functional.
Pour que le greffon polyamide ait une terminaison monoamine, il suffit d'utiliser un limiteur de chaîne de formule : In order for the polyamide graft to have a monoamine termination, it suffices to use a chain limiter of formula:
R 1 †I H R 1 † IH
R  R
2 dans laquelle :  2 in which:
RI est l'hydrogène ou un groupement alkyle linéaire ou ramifié contenant jusqu'à 20 atomes de carbone, RI is hydrogen or a linear or branched alkyl group containing up to 20 carbon atoms,
R2 est un groupement ayant jusqu'à 20 atomes de carbone alkyle ou alcényle linéaire ou ramifié, un radical cycloaliphatique saturé ou non, un radical aromatique ou une combinaison des précédents. Le limiteur peut être, par exemple, la laurylamine ou l'oleylamine. R2 is a group having up to 20 linear or branched alkyl or alkenyl carbon atoms, a saturated or unsaturated cycloaliphatic radical, an aromatic radical or a combination of the foregoing. The limiter may be, for example, laurylamine or oleylamine.
Pour que le greffon polyamide ait une terminaison monoacide carboxylique, il suffit d'utiliser un limiteur de chaîne de formule R' 1-COOH, R' l-CO-O-CO-R'2 ou un diacide carboxylique. R' I et R'2 sont des groupements alkyles linéaires ou ramifiés contenant jusqu'à 20 atomes de carbone. For the polyamide graft to have a monocarboxylic acid terminus, it is sufficient to use a chain-limiting agent of the formula R '1 -COOH, R' 1 -CO-O-CO-R'2 or a dicarboxylic acid. R 'I and R'2 are linear or branched alkyl groups containing up to 20 carbon atoms.
Avantageusement, le greffon polyamide possède une extrémité à fonctionnalité aminé. Les limiteurs monofonctionnels de polymérisation préférés sont la laurylamine et l'oléy lamine. Advantageously, the polyamide graft has an amino functional end. The preferred monofunctional polymerization limiters are laurylamine and oleylamine.
Les greffons polyamides ont une masse molaire comprise entre 1000 et 10000 g/mol. Etant donné que le rapport stœchio métrique pour le greffage des greffons polyamide sur le tronc polyoléfme est constant, le choix de la masse des greffons polyamide est fonction de la masse de polyamide désirée dans la composition selon ce qui a été expliqué précédemment. The polyamide grafts have a molar mass of between 1000 and 10000 g / mol. Since the stoichiometric ratio for the grafting of the polyamide grafts on the polyolefin trunk is constant, the choice of the mass of the polyamide grafts is a function of the mass of polyamide desired in the composition as explained above.
Il suffira à l'homme du métier de sélectionner les types et ratio de monomères ainsi que choisir les masses molaires des greffons polyamide pour pouvoir obtenir aisément les valeurs voulues de température de transition vitreuse, éventuellement de température de fusion ainsi que de viscosité du greffon polyamide. La réaction de condensation du greffon polyamide sur le tronc de polyoléfme contenant le reste de X s'effectue par réaction d'une fonction aminé ou acide du greffon polyamide sur le reste de X. Avantageusement, on utilise des greffons polyamide monoamine et on crée des liaisons amides ou imides en faisant réagir la fonction aminé sur la fonction du reste de X. On réalise cette condensation de préférence à l'état fondu. Pour fabriquer la composition selon l'invention, on peut utiliser les techniques classiques de malaxage et/ou d'extrusion. Les composants de la composition sont ainsi mélangés pour former un compound qui pourra éventuellement être granulé en sortie de filière. Avantageusement, des agents de couplage sont ajoutés lors du compoundage. Pour obtenir une composition nanostructurée, on peut ainsi mélanger le greffon polyamide et le tronc dans une extrudeuse, à une température généralement comprise entre 200 et 300 °C. Le temps de séjour moyen de la matière fondue dans l'extrudeuse peut être compris entre 5 secondes et 5 minutes, et de préférence entre 20 secondes et 1 minute. Le rendement de cette réaction de condensation est évalué par extraction sélective des greffons de polyamide libres, c'est-à-dire ceux qui n'ont pas réagi pour former le polymère greffé polyamide. La préparation de greffons polyamide à extrémité aminé ainsi que leur addition sur un tronc de polyoléfme contenant le reste de (X) est décrite dans les brevets US3976720, US3963799, US5342886 et FR2291225. Le polymère greffé polyamide de la présente invention présente avantageusement une organisation nanostructurée. It will be sufficient for a person skilled in the art to select the types and ratio of monomers as well as to choose the molar masses of the polyamide grafts in order to easily obtain the desired values of glass transition temperature, possibly of melting temperature, as well as viscosity of the polyamide graft. . The condensation reaction of the polyamide graft on the polyolefin trunk containing the remainder of X is carried out by reaction of an amine or acid function of the polyamide graft on the remainder of X. Advantageously, polyamide monoamine grafts are used and amide or imide bonds by reacting the amine function on the function of the remainder of X. This condensation is preferably carried out in the molten state. To manufacture the composition according to the invention, conventional kneading and / or extrusion techniques can be used. The components of the composition are thus mixed to form a compound which may optionally be granulated at the die outlet. Advantageously, coupling agents are added during compounding. To obtain a nanostructured composition, it is thus possible to mix the polyamide graft and the trunk in an extruder at a temperature generally of between 200 and 300 ° C. The average residence time of the melt in the extruder can be between 5 seconds and 5 minutes, and preferably between 20 seconds and 1 minute. The yield of this condensation reaction is evaluated by selective extraction of the free polyamide grafts, that is to say those which have not reacted to form the polyamide graft polymer. The preparation of aminated end polyamide grafts and their addition to a polyolefin trunk containing the remainder of (X) is described in US3976720, US3963799, US5342886 and FR2291225. The polyamide graft polymer of the present invention advantageously has a nanostructured organization.
S'agissant du second polymère, il s'agit d'un - le second polymère, présent dans la composition entre 10 % et 90 % en poids, consiste en un copolymère d'éthylène et d'un comonomère non réactif ou non fonctionnalisé dont le module élastique en flexion est inférieur à 250 Mpa à 23°C et qui présente un point de fusion cristalline compris entre 60°C et 120°C. With regard to the second polymer, it is a - the second polymer, present in the composition between 10% and 90% by weight, consists of a copolymer of ethylene and a non-reactive or non-functional comonomer of which the bending elastic modulus is less than 250 MPa at 23 ° C and has a crystalline melting point of between 60 ° C and 120 ° C.
Avantageusement, selon un mode d'exécution, ce second polymère consiste en un copolymère de l'éthylène et d'un (méth)acrylate d'alkyle.  Advantageously, according to one embodiment, this second polymer consists of a copolymer of ethylene and an alkyl (meth) acrylate.
Autrement dit, ce second polymère consiste en un homopolymère d'une oléfme ou un copolymère d'au moins une alphaoléfme et d'au moins un autre monomère copolymérisable, pourvu bien sûr que les conditions de module et de point de fusion cristalline soient respectés.  In other words, this second polymer consists of a homopolymer of an olefin or a copolymer of at least one alphaolefin and at least one other copolymerizable monomer, provided of course that the conditions of modulus and crystalline melting point are met.
Avantageusement la polyoléfme souple est choisie parmi les polyéthylènes homo- ou copolymères.  Advantageously, the flexible polyolefin is chosen from homo- or copolymeric polyethylenes.
A titre de comonomères, on peut citer :  As comonomers, we can mention:
- les alpha-oléfmes, avantageusement celles ayant de 3 à 30 atomes de carbone. alpha-olefins, advantageously those having from 3 to 30 carbon atoms.
Des exemples d' alpha-oléfmes ayant 3 à 30 atomes de carbone comme comonomères éventuels comprennent le propylène, 1 -butène, 1-pentène, 3-méthyl-l- butène, 1-hexène, 4-méthyl- 1-pentène, 3-méthyl- 1-pentène, 1-octène, 1 -décène, 1- dodécène, 1-tétradécène, 1-hexadécène, 1-octadécène, 1— eicocène, 1-dococène, 1- tétracocène, 1-hexacocène, 1— octacocène, et 1-triacontène. Ces alpha-oléfmes peuvent être utilisées seules ou en mélange de deux ou de plus de deux. Examples of alpha-olefins having 3 to 30 carbon atoms as optional comonomers include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3 1-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, 1-dococene, 1-tetracocene, 1-hexacocene, 1-octacocene , and 1-triacontene. These alpha-olefins can be used alone or in a mixture of two or more than two.
- les esters d'acides carboxyliques insaturés tels que par exemple les (méth)acrylates d'alkyle, les alkyles pouvant avoir jusqu'à 24 atomes de carbone.  esters of unsaturated carboxylic acids such as, for example, alkyl (meth) acrylates, the alkyls having up to 24 carbon atoms.
Des exemples d'acrylate ou méthacrylate d'alkyle sont notamment le méthacrylate de méthyle, l'acrylate d'éthyle, l'acrylate de n-butyle, l'acrylate d'isobutyle, l'acrylate de 2-éthylhexyle. - les esters vinyliques d'acides carboxyliques saturés tels que par exemple l'acétate ou le propionate de vinyle. Examples of alkyl acrylate or methacrylate include methyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate and 2-ethylhexyl acrylate. vinyl esters of saturated carboxylic acids such as, for example, acetate or vinyl propionate.
- les diènes tels que par exemple le 1,4-hexadiène.  dienes such as, for example, 1,4-hexadiene.
La polyoléfme souple peut comprendre plusieurs comonomères.  The flexible polyolefin may comprise several comonomers.
A titre d'exemple on peut citer :  By way of example, mention may be made of:
- le polyéthylène basse densité (LDPE)  - low density polyethylene (LDPE)
- le polyéthylène linéaire basse densité (LLDPE)  - linear low density polyethylene (LLDPE)
- le polyéthylène très basse densité (VLDPE)  - very low density polyethylene (VLDPE)
- le polyéthylène obtenu par catalyse métallocène, c'est-à-dire les polymères obtenus par copolymérisation d'éthylène et d'alphaoléfïne telle que propylène, butène, héxène ou octène en présence d'un catalyseur monosite constitué généralement d'un atome de zirconium ou de titane et de deux molécules cycliques alkyles liées au métal. Plus spécifiquement, les catalyseurs métallocènes sont habituellement composés de deux cycles cyclopentadiéniques liés au métal. Ces catalyseurs sont fréquemment utilisés avec des aluminoxanes comme cocatalyseurs ou activateurs, de préférence le méthylaluminoxane (MAO). Le hafnium peut aussi être utilisé comme métal auquel le cyclopentadiène est fixé. D'autres métallocènes peuvent inclure des métaux de transition des groupes IV A, V A, et VI A. Des métaux de la série des lanthamides peuvent aussi être utilisés.  polyethylene obtained by metallocene catalysis, that is to say polymers obtained by copolymerization of ethylene and alphaolefin such as propylene, butene, hexene or octene in the presence of a monosite catalyst generally consisting of a zirconium or titanium and two alkyl cyclic molecules bonded to the metal. More specifically, metallocene catalysts are usually composed of two metal-bound cyclopentadiene rings. These catalysts are frequently used with aluminoxanes as cocatalysts or activators, preferably methylaluminoxane (MAO). Hafnium may also be used as the metal to which cyclopentadiene is attached. Other metallocenes may include transition metals of groups IV A, V A, and VI A. Metals of the lanthamide series may also be used.
- les élastomères EPR (éthylène - propylène - rubber)  - EPR elastomers (ethylene - propylene - rubber)
- les élastomères EPDM (éthylène - propylène - diène)  EPDM elastomers (ethylene-propylene-diene)
- les mélanges de polyéthylène avec un EPR ou un EPDM  - Polyethylene blends with EPR or EPDM
- les copolymères éthylène-(méth)acrylate d'alkyle pouvant contenir jusqu'à 60% en poids de (méth)acrylate et de préférence 2 à 40%  ethylene-alkyl (meth) acrylate copolymers which may contain up to 60% by weight of (meth) acrylate and preferably 2 to 40%
A titre d'exemple on peut citer les copolymères souples de l'éthylène tels que les copolymères obtenus par voie radicalaire sous haute pression de l'éthylène avec de l'acétate de vinyle, des esters (meth)acryliques de l'acide (meth)acrylique et d'un alcool ayant de 1 à 24 atomes de carbone et avantageusement de 1 à 9, les terpolymères radicalaires utilisant en plus un troisième monomère choisi par les monomères insaturés copolymérisables avec l'éthylène tels que l'acide acrylique, l'anhydride maléique, le méthacrylate de glycidyle. Ces copolymères souples peuvent aussi être des copolymères de l'éthylène avec des alfa-oléfïnes de 3 à 8 atomes de carbone tels que les EPR, les copolymères de très basse densité de l'éthylène avec du butène de l'hexène ou de l'octène de densité comprise entre 0.870 et 0.910 g/cm3 obtenues par catalyse metallocène ou Ziegler - Natta. Par polyoléfmes souples , nous entendons également les mélanges de 2 ou plusieurs polyoléfmes souples. By way of example, mention may be made of flexible copolymers of ethylene such as copolymers obtained by high pressure radical formation of ethylene with vinyl acetate, (meth) acrylic acid esters (meth) ) and an alcohol having from 1 to 24 carbon atoms and preferably from 1 to 9, the radical terpolymers also using a third monomer chosen from unsaturated monomers copolymerizable with ethylene such as acrylic acid, maleic anhydride, glycidyl methacrylate. These flexible copolymers can also be copolymers of ethylene with alfa-olefins of 3 to 8 carbon atoms, such as EPRs, ethylene very low density copolymers with butene of hexene or of octene with a density of between 0.870 and 0.910 g / cm 3 obtained by metallocene or Ziegler-Natta catalysis. By flexible polyolefms we also mean mixtures of 2 or more flexible polyolefms.
L'invention est particulièrement utile pour les copolymères de l'éthylène et des (méth)acrylates d'alkyle. L'alkyle peut avoir jusqu'à 24 atomes de carbone. De préférence les (méth)acrylates sont choisis parmi ceux cités plus haut. Ces copolymères comprennent avantageusement jusqu'à 40 % en poids de (méth)acrylate et de préférence 3 à 35 %. Leur MFI est avantageusement compris entre 0,1 et 50 (à 190°C - 2,16 kg).  The invention is particularly useful for copolymers of ethylene and alkyl (meth) acrylates. The alkyl can have up to 24 carbon atoms. Preferably the (meth) acrylates are chosen from those mentioned above. These copolymers advantageously comprise up to 40% by weight of (meth) acrylate and preferably 3 to 35%. Their MFI is advantageously between 0.1 and 50 (at 190 ° C. - 2.16 kg).
Avantageusement, le module de flexion est compris entre 5 et 150 MPa.  Advantageously, the flexural modulus is between 5 and 150 MPa.
S'agissant du troisième polymère, optionnel selon l'invention, il s'agit d'une polyoléfïne fonctionnalisée comprenant un copolymère d'au moins une alpha-oléfme, telle que l'éthylène ou le propylène, avec au moins un comonomère portant une fonction réactive, choisi notamment parmi un acide carboxylique, tel que l'acide (méth)acrylique, un anhydride carboxylique, tel que l'anhydride maléique, ou un époxyde, tel que le (méth)acrylate de glycidyle, et au moins un autre comonomère ne portant pas de fonction réactive, choisi par exemple parmi une alpha-oléfme différente ; un diène tel que le butadiène ; un ester d'acide carboxylique insaturé, tel qu'un (méth)acrylate d'alkyle où le groupe alkyle peut être un groupe méthyle, éthyle ou butyle, notamment ; et un ester vinylique d'acide carboxylique, tel que l'acétate de vinyle. As regards the third optional polymer according to the invention, it is a functionalized polyolefin comprising a copolymer of at least one alpha-olefin, such as ethylene or propylene, with at least one comonomer carrying a reactive function, chosen especially from a carboxylic acid, such as (meth) acrylic acid, a carboxylic anhydride, such as maleic anhydride, or an epoxide, such as glycidyl (meth) acrylate, and at least one other comonomer not carrying a reactive function, chosen for example from a different alpha-olefin; a diene such as butadiene; an unsaturated carboxylic acid ester, such as an alkyl (meth) acrylate wherein the alkyl group may be a methyl, ethyl or butyl group, especially; and a vinyl ester of carboxylic acid, such as vinyl acetate.
A titre d'exemple de comonomère réactif on peut citer :  As an example of a reactive comonomer, mention may be made of:
- les époxydes insaturés.  unsaturated epoxides.
Des exemples d' époxydes insaturés sont notamment :  Examples of unsaturated epoxides include:
- les esters et éthers de glycidyle aliphatiques tels que Pallylglycidyléther, le vinylglycidyléther, le maléate et l'itaconate de glycidyle, l'acrylate et le méthacrylate de glycidyle, et  aliphatic glycidyl esters and ethers such as allyl glycidyl ether, vinyl glycidyl ether, glycidyl maleate and itaconate, acrylate and glycidyl methacrylate, and
- les esters et éthers de glycidyle alicycliques tels que le 2-cyclohexène-l- glycidyléther, le cyclohexène-4,5-diglycidylcarboxylate, le cyclohexène-4-glycidyl carboxylate, le 5-norbornène-2-méthyl-2-glycidyl carboxylate et l'endocis- bicyclo(2,2,l)-5-heptène-2,3-diglycidyl dicarboxylate.  alicyclic glycidyl esters and ethers such as 2-cyclohexene-1-glycidyl ether, cyclohexene-4,5-diglycidylcarboxylate, cyclohexene-4-glycidyl carboxylate, 5-norbornene-2-methyl-2-glycidyl carboxylate and endocisbicyclo (2,2,1) -5-heptene-2,3-diglycidyl dicarboxylate.
- les acides carboxyliques insaturés, leurs sels, leurs anhydrides. Des exemples d'anhydrides d'acide dicarboxylique insaturé sont notamment l'anhydride maléique, l'anhydride itaconique, l'anhydride citraconique, l'anhydride tétrahydrophtalique . A titre d'exemple de copolymère comprenant un comonomère réactif on peut citer : unsaturated carboxylic acids, their salts, their anhydrides. Examples of unsaturated dicarboxylic acid anhydrides include maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride. By way of example of a copolymer comprising a reactive comonomer, mention may be made of:
- les copolymères éthylène (méth)acrylate d'alkyle-anhydride maléique obtenus par copolymérisation des trois monomères, les proportions de (méth)acrylate étant comme les copolymères ci-dessus, la quantité d'anhydride maléique étant jusqu'à 10% et de préférence 0,2 à 6% en poids.  the ethylene (meth) acrylate-maleic anhydride copolymers obtained by copolymerization of the three monomers, the proportions of (meth) acrylate being as the above copolymers, the amount of maleic anhydride being up to 10% and of preferably 0.2 to 6% by weight.
- les copolymères éthylène-acétate de vinyle-anhydride maléique obtenus par copolymérisation des trois monomères, les proportions étant les mêmes que dans le copolymère précédent.  the ethylene-vinyl acetate-maleic anhydride copolymers obtained by copolymerization of the three monomers, the proportions being the same as in the preceding copolymer.
On préfère que la polyoléfme fonctionnalisée renferme de 60 à 100% en poids d'alpha-oléfme et de 0 à 40%> en poids, de préférence de 0 à 15% en poids, de comonomère ne portant pas de fonction réactive. On préfère en outre que la polyoléfme fonctionnalisée renferme de 0,1 à 15% en poids, de préférence de 0,5 à 5% en poids, de comonomère portant une fonction réactive. Des exemples de telles polyoléfînes fonctionnalisées sont les copolymères éthylène / ester acrylique / méthacrylate de glycidyle et éthylène / ester acrylique / anhydride maléique, respectivement disponibles auprès de la société ARKEMA sous la dénomination commerciale Lotader® GMA et Lotader® MAH. It is preferred that the functionalized polyolefin contain from 60 to 100% by weight of alpha-olefin and from 0 to 40% by weight, preferably from 0 to 15% by weight, of comonomer not carrying a reactive function. It is further preferred that the functionalized polyolefin contain from 0.1 to 15% by weight, preferably from 0.5 to 5% by weight, of comonomer carrying a reactive function. Examples of such polyolefins are functionalized ethylene / acrylic ester / glycidyl methacrylate and ethylene / acrylic ester / maleic anhydride, respectively available from Arkema under the trade name Lotader ® GMA and Lotader ® MAH.
Des compléments, ou adjuvants, pourront éventuellement être ajoutés à la composition selon l'invention afin de conférer à cette dernière telle ou telle fonctionnalité complémentaire. Complements, or adjuvants, may optionally be added to the composition according to the invention in order to confer on the latter such or such complementary functionality.
Dans cette application particulière de la composition aux modules photovoltaïques, le rayonnement UV (Ultra Violet) étant susceptible d'entraîner un léger jaunissement de la composition utilisée, des stabilisants UV et des absorbeurs UV tels que le benzotriazole, le benzophénone et les autres aminés encombrés, peuvent être ajoutés afin d'assurer la transparence de l'encapsulant durant sa durée de vie. Ces composés peuvent être par exemple à base de benzophénone ou de benzotriazole. On peut les ajouter dans des quantités inférieures à 10% en masse de la masse totale de la composition et préférentiellement de 0, 1 à 5%. In this particular application of the composition to photovoltaic modules, the UV radiation (Ultra Violet) is likely to cause a slight yellowing of the composition used, UV stabilizers and UV absorbers such as benzotriazole, benzophenone and other hindered amines , can be added to ensure the transparency of the encapsulant during its lifetime. These compounds may for example be based on benzophenone or benzotriazole. We may be added in amounts less than 10% by weight of the total mass of the composition and preferably from 0.1 to 5%.
On pourra également ajouter des antioxydants pour limiter le jaunissement lors de la fabrication de l'encapsulant tels que les composés phosphorés (phosphonites et/ou phosphites) et les phénoliques encombrés. On peut ajouter ces antioxydants dans des quantités inférieures à 10% en masse de la masse totale de la composition et préférentiellement de 0,1 à 5%.  It is also possible to add antioxidants to limit yellowing during the manufacture of the encapsulant such as phosphorus compounds (phosphonites and / or phosphites) and hindered phenolics. These antioxidants may be added in amounts of less than 10% by weight of the total mass of the composition and preferably from 0.1 to 5%.
Des agents retardateurs de flamme peuvent également être ajoutés. Ces agents peuvent être halogénés ou non-halogénés. Parmi les agents halogénés, on peut citer les produits bromés. On peut également utiliser comme agent non-halogéné les additifs à base de phosphore tels que le phosphate d'ammonium, de polyphosphate, de phosphinate ou de pyrophosphate, le cyanurate de mélamine, le pentaérythritol, les zéolithes ainsi que les mélanges de ces agents. La composition peut comprendre ces agents dans des proportions allant de 3 à 40% par rapport à la masse totale de la composition. Flame retardants may also be added. These agents may be halogenated or non-halogenated. Among the halogenated agents, mention may be made of brominated products. Phosphorus-based additives such as ammonium phosphate, polyphosphate phosphate, phosphinate or pyrophosphate phosphate, melamine cyanurate, pentaerythritol, zeolites and mixtures of these agents may also be used as non-halogenated agents. The composition may comprise these agents in proportions ranging from 3 to 40% relative to the total mass of the composition.
Si cela est souhaité dans une application particulière, on peut également ajouter des pigments comme par exemple des composés colorants ou azurants dans des proportions allant généralement de 5 à 15% par rapport à la masse totale de la composition. Concernant les autres aspects de l'invention relatifs à l'utilisation de la composition selon l'invention dans un module photovoltaïque, l'Homme de l'Art peut se référer par exemple au « Handbook of Photovoltaic Science and Engineering », Wiley, 2003 volume 7. If desired in a particular application, it is also possible to add pigments such as coloring or brightening compounds in proportions generally ranging from 5 to 15% relative to the total weight of the composition. Regarding the other aspects of the invention relating to the use of the composition according to the invention in a photovoltaic module, one skilled in the art can refer for example to the "Handbook of Photovoltaic Science and Engineering", Wiley, 2003 volume 7.
Préparation de la composition selon l'invention : Preparation of the composition according to the invention
La technique de greffage des greffons polyamide sur le tronc polyoléfme pour obtenir la polyoléfme greffé polyamide selon l'invention est bien connu de l'homme du métier, et notamment des documents cités précédemment FR 2912150, FR 2918150 ou EP 21966489. On ne sort donc pas du cadre de l'invention si des agents réticulant sont ajoutés. On peut citer comme exemples des isocyanates ou des peroxydes organiques. Cette réticulation peut également être réalisée par des techniques connues d'irradiation. Cette réticulation peut être effectuée par l'une des nombreuses méthodes connues de l'homme du métier, notamment par l'utilisation d'initiateurs activés thermiquement, par exemple des composés peroxydes et azo, des photoinitiateurs tels que le benzophénone, par des techniques de radiation comportant des rayons lumineux, des rayons UV, des faisceaux d'électrons et des rayons X, de silanes porteurs de fonctions réactives comme un amino silane, un époxy silane, un vinyle silane tel que par exemple le vinyle silane tri-éthoxy ou tri-méthoxy, et de la réticulation par voie humide. Le manuel intitulé « Handbook of polymer foams and technology » supra, aux pages 198 à 204, fournit des enseignements complémentaires auxquels l'homme du métier peut se référer. The grafting technique of polyamide grafts on the polyolefin trunk to obtain the polyamide graft polyolefin according to the invention is well known to those skilled in the art, and in particular the documents cited above FR 2912150, FR 2918150 or EP 21966489. It is not beyond the scope of the invention if crosslinking agents are added. Examples are isocyanates or organic peroxides. This crosslinking can also be carried out by known techniques of irradiation. This crosslinking can be carried out by one of the many methods known to those skilled in the art, in particular by the use of thermally activated initiators, for example peroxide and azo compounds, photoinitiators such as benzophenone, by radiation comprising light rays, UV rays, electron beams and X-rays, silanes carrying reactive functional groups such as an amino silane, an epoxy silane, a vinyl silane such as, for example, vinyl silane tri-ethoxy or tri methoxy, and wet crosslinking. The manual entitled "Handbook of polymer foams and technology" supra, at pages 198 to 204, provides complementary teachings to which a person skilled in the art can refer.
Concernant les aspects de l'invention relatifs à l'utilisation de la composition thermoplastique dans un module photovoltaïque, l'Homme de l'Art peut se référer par exemple au Handbook of Photo voltaic Science and Engineering, Wiley, 2003. En effet, la composition de l'invention peut être utilisée en tant qu'encapsulant ou encapsulant- backsheet dans un module photovoltaïque, dont on décrit la structure en relation avec les figures annexées. Regarding the aspects of the invention relating to the use of the thermoplastic composition in a photovoltaic module, one skilled in the art can refer for example to the Handbook of Photo Voltaic Science and Engineering, Wiley, 2003. Indeed, the composition of the invention can be used as an encapsulant or encapsulant-backsheet in a photovoltaic module, the structure of which is described in relation to the appended figures.
Matériaux employés pour former les formulations testées : Materials used to form the tested formulations:
Lotader 7500: terpolymère d'éthylène, d'acrylate d'éthyle (17,5 % en poids) et d'anhydride maléique (2,8 % en poids) produit par ARKEMA possédant un MFI (190°C sous 2,16 kg mesuré selon ISO 1133) de 70 g/10 mn (minute). Lotader 7500: terpolymer of ethylene, ethyl acrylate (17.5% by weight) and maleic anhydride (2.8% by weight) produced by ARKEMA having an MFI (190 ° C. under 2.16 kg) measured according to ISO 1133) of 70 g / 10 min (minute).
Lotader 5500: terpolymère d'éthylène, d'acrylate d'éthyle (20 % en poids) et d'anhydride maléique (2,8 % en poids) produit par ARKEMA possédant un MFI (190°C sous 2,16 kg mesuré selon ISO 1133) de 20 g/10 mn.  Lotader 5500: terpolymer of ethylene, ethyl acrylate (20% by weight) and maleic anhydride (2.8% by weight) produced by ARKEMA having an MFI (190 ° C. under 2.16 kg, measured according to ISO 1133) of 20 g / 10 min.
Lotryl 17 BA07: copolymère d'éthylène et d'acrylate de butyle (17 % en poids) produit par ARKEMA possédant un MFI (190°C sous 2,16 kg mesuré selon ISO 1133) de 7 g/ 10 mn.  Lotryl 17 BA07: copolymer of ethylene and butyl acrylate (17% by weight) produced by ARKEMA having an MFI (190 ° C. under 2.16 kg measured according to ISO 1133) of 7 g / 10 min.
Lotryl 18MA02: copolymère d'éthylène et d'acrylate de méthyle (18 % en poids) produit par ARKEMA possédant un MFI (190°C sous 2,16 kg mesuré selon ISO 1133) de 2 g/10 mn. Elvaloy AC 1820 : copolymère d'éthylène et d'acrylate de méthyle (20 % en poids) produit par Dupont possédant un MFI (190°C sous 2, 16 kg mesuré selon ISO 1 133) de 8 g/10 ma Lotryl 18MA02: copolymer of ethylene and methyl acrylate (18% by weight) produced by ARKEMA having an MFI (190 ° C. under 2.16 kg measured according to ISO 1133) of 2 g / 10 min. Elvaloy AC 1820: copolymer of ethylene and methyl acrylate (20% by weight) produced by Dupont having an MFI (190 ° C. under 2.16 kg measured according to ISO 1133) of 8 g / 10 m
Prépolymère PA6 : Un prépolymère PA6 a été synthétisé par polycondensation à partir du lactame 6. La laurylamine est utilisée comme limitateur de chaîne de façon à avoir une seule fonctionnalité aminé primaire en bout de chaîne. La masse molaire moyenne en nombre du premier prépolymère est de 2500 g/mol.  Prepolymer PA6: A PA6 prepolymer was synthesized by polycondensation from lactam 6. Laurylamine is used as a chain limiter so as to have a single primary amine functionality at the end of the chain. The number-average molar mass of the first prepolymer is 2500 g / mol.
Prépolymère copolyamide 6/12 à température de fusion 130°C : un prépolymère copolyamide 6/12 a été synthétisé par polycondensation à partir du lactame 6 et du lactame 12. Le ratio lactame 6/lactame 12 est ajusté pour obtenir une température de fusion de 130°C. La laurylamine est utilisée comme limitateur de chaîne de façon à avoir une seule fonctionnalité aminé primaire en bout de chaîne. Sa masse molaire moyenne en nombre est de 2500 g/mol.  6/12 copolyamide prepolymer at melting temperature 130 ° C: a 6/12 copolyamide prepolymer was synthesized by polycondensation from lactam 6 and lactam 12. The lactam 6 / lactam ratio 12 is adjusted to obtain a melting temperature of 130 ° C. Laurylamine is used as a chain limiter to have a single primary amine functionality at the end of the chain. Its average molar mass is 2500 g / mol.
Prépolymère copolyamide 6/11 à température de fusion 150°C : un prépolymère copolyamide 6/1 1 a été synthétisé par polycondensation à partir du lactame 6 et de l'amino 1 1. Le ratio lactame 6/amino 1 1 est ajusté pour obtenir une température de fusion de 150°C. La laurylamine est utilisée comme limitateur de chaîne de façon à avoir une seule fonctionnalité aminé primaire en bout de chaîne. Sa masse molaire moyenne en nombre est de 3200 g/mol.  6/11 copolyamide prepolymer at melting temperature 150 ° C: a 6/1 1 copolyamide prepolymer was synthesized by polycondensation from lactam 6 and amino 1 1. The lactam 6 / amino 1 1 ratio was adjusted to obtain a melting temperature of 150 ° C. Laurylamine is used as a chain limiter to have a single primary amine functionality at the end of the chain. Its average molar mass is 3200 g / mol.
Apolhya : La famille Apolhya est une famille de polymères commercialisée par Apolhya: The Apolhya family is a family of polymers marketed by
ARKEMA qui allient les propriétés des polyamides à celles des polyoléfïnes grâce à l'obtention de morphologies co-continues à l'échelle manométrique. Dans le cadre des tests, il est retenu plusieurs types d' Apolhya® : ARKEMA, which combines the properties of polyamides with those of polyolefins by obtaining co-continuous morphologies on a manometric scale. As part of the tests, several types of Apolhya ® are selected:
• Apolhya A sur la base du Lotader® 7500 et du copolyamide 6/12 de température de fusion de 130°C contenant 20% en poids de copolyamide. • Apolhya A on the basis of Lotader ® 7500 and the melting temperature of copolyamide 6/12 of 130 ° C containing 20% by weight of copolyamide.
• Apolhya B sur la base du Lotader® 7500 et du copolyamide 6/1 1 de température de fusion de 150°C contenant 20% en poids de polyamide. • Apolhya B on the basis of Lotader ® 7500 and copolyamide 6/1 1 melting temperature of 150 ° C containing 20% by weight of polyamide.
• Apolhya C sur la base du Lotader® 7500 et du polyamide 6 de température de fusion de 220°C contenant 20%> en poids de polyamide. • Apolhya C on the basis of Lotader ® 7500 and polyamide 6 melt temperature of 220 ° C containing 20%> by weight of polyamide.
· Apolhya D sur la base du Lotader® 7500 et du polyamide 1 1 de température de fusion de 190°C contenant 20%> en poids de copolyamide. Apolhya · D on the basis of Lotader ® 7500 and January 1 polyamide melting temperature of 190 ° C containing 20%> by weight of copolyamide.
• Apolhya E sur la base du Lotader® 7500 et du polyamide 6/12 de température de fusion de 130°C contenant 50%> en poids de copolyamide. • Apolhya F sur la base du Lotader® 5500 et du polyamide 6/12 de température de fusion de 130°C contenant 20% en poids de copolyamide. • Apolhya E on the basis of Lotader ® 7500 and 6/12 polyamide melting temperature of 130 ° C containing 50%> by weight of copolyamide. • Apolhya F on the basis of Lotader ® 5500 and 6/12 polyamide melting temperature of 130 ° C containing 20% by weight of copolyamide.
Taux de Rate
Lotryl Lotryl Elvaloy  Lotryl Lotryl Elvaloy
polyamide dans Apolhya Lotader 5500 Lotader 7500 polyamide in Apolhya Lotader 5500 Lotader 7500
Compositions 17BA07 18MA02 AC 1820 Compositions 17BA07 18MA02 AC 1820
la composition  the composition
(% massique)  (% by mass)
A B C D E F  A B C D E F
Exemple 1 3,5 17,5 72,5 10  Example 1 3.5 17.5 72.5 10
Exemple 2 6 30 60 10  Example 2 6 30 60 10
Exemple 3 11 55 35 10 Example 3 11 55 35 10
Exemple 4 11 55 35 10Example 4 11 55 35 10
Exemple 5 12,5 62,5 27,5 10 Example 5 12.5 62.5 27.5 10
Exemple 6 8 16 60 24  Example 6 8 16 60 24
Exemple 7 8 16 60 24  Example 7 8 16 60 24
37,  37
Exemple 8 7,5 12,5 40 10  Example 8 7.5 12.5 40 10
5  5
Exemple 9 8 40 50 10 Example 9 8 40 50 10
Exemple 10 8 16 79 5Example 10 8 16 79 5
Exemple comparatif 1 2 10 90 Comparative Example 1 2 10 90
Exemple comparatif 2 17 85 15  Comparative Example 2 17 85 15
Exemple comparatif 3 20 100  Comparative Example 3
Exemple comparatif 4 13 65 35  Comparative Example 4 13 65 35
Exemple comparatif 5 13 65 35 Comparative Example 5 13 65 35
Obtention des formulations et films testés : Obtaining formulations and films tested:
• Extrusion réactive des formulations o Extrusion réactive des formulations Apolhya sur base Lotader 7500 ou Lotader 5000 et copolyamides 6/12 et 6/11 • Reactive extrusion of formulations o Reactive extrusion of Apolhya formulations based on Lotader 7500 or Lotader 5000 and copolyamides 6/12 and 6/11
Ces formulations Apolhya ont été préparées par « compoundage » grâce à une extrudeuse double vis co-rotative de type Leistritz® (L/D=35) dont les éléments de fourreaux sont chauffés selon un profil plat à 190°C; la vitesse de rotation est de 300 rpm (« round per minute » ou Tour Par Minute) avec un débit de 15 kg/h (kilogramme par heure). o Extrusion réactive des formulations Apolhya sur base Lotader 7500 et polyamide 6 These Apolhya formulations were prepared by "compounding" by means of a Leistritz®-type co-rotating twin-screw extruder (L / D = 35) whose pipe elements were heated to a flat profile at 190 ° C .; the rotation speed is 300 rpm ("round per minute" or "Tour Per Minute") with a flow rate of 15 kg / h (kilogram per hour). o Reactive extrusion of Apolhya formulations based on Lotader 7500 and polyamide 6
Ces formulations Apolhya ont été préparées par « compoundage » grâce à une extrudeuse double vis co-rotative de type Leistritz® (L/D=35) dont les éléments de fourreaux sont chauffés selon un profil plat à 240°C ; la vitesse de rotation est de 300 rpm (« round per minute » ou Tour Par Minute) avec un débit de 15 kg/h (kilogramme par heure). These Apolhya formulations were prepared by "compounding" by means of a Leistritz®-type co-rotating twin-screw extruder (L / D = 35) whose pipe elements were heated to a flat profile at 240 ° C .; the rotation speed is 300 rpm ("round per minute" or "Tour Per Minute") with a flow rate of 15 kg / h (kilogram per hour).
• Extrusion de films monocouches de 400 μηι des compositions Apolhya/polyoléfinefs) de l'invention et des exemples comparatifs  Extrusion of monolayer films of 400 μηι of the Apolhya / polyolefin compositions of the invention and comparative examples
Des films monocouches de 400 μιη (micromètre) ont été réalisés par extrusion de film à plat sur une petite ligne d' extrusion de laboratoire. Les compositions sont obtenues par mélange d'une polyoléfïne greffée polyamide, d'un copolymère d'éthylène et d'un acrylate d'alkyle et éventuellement d'une troisième polyoléfïne fonctionnalisée à l'anhydride maléique. Les proportions entre les constituants sont assurées en réalisant un mélange à sec en sac des granulés préalable à Γ extrusion. Monolayer films of 400 μιη (micrometer) were made by extrusion of flat film on a small laboratory extrusion line. The compositions are obtained by mixing a polyamide grafted polyolefin, a copolymer of ethylene and an alkyl acrylate and optionally a third polyolefin functionalized with maleic anhydride. The proportions between the constituents are ensured by carrying out a dry bag mix of the granules prior to extrusion.
L'extrudeuse est une bi-vis contrarotative de type Haake 1 équipée d'une filière plate de 10 cm (centimètre) de large et de 0,5 mm (millimètre) d'ouverture. Les éléments de fourreaux sont chauffés selon un profil plat à 160°C pour les exemples illustratifs de l'invention à base de copolyamide 6/12 ; la vitesse de rotation des vis étant de 60 rpm (tour par minute ou « round per minute »). Pour les contre-exemples de l'invention à base de polyamide 6, les éléments de fourreaux sont chauffés selon un profil plat à 220° C la vitesse de rotation des vis étant de 60 rpm. Pour les contre- exemples de l'invention à base de polyamide 6/11, les éléments de fourreaux sont chauffés selon un profil plat à 180°C, la vitesse de rotation des vis étant de 60 rpm. The extruder is a Haake 1 contra-rotating twin-screw equipped with a flat die 10 cm (cm) wide and 0.5 mm (mm) aperture. The pipe elements are heated in a flat profile at 160 ° C for the illustrative examples of the invention based on copolyamide 6/12; the speed of rotation of the screws being 60 rpm (round per minute or "round per minute"). For counterexamples of the polyamide-based invention, the pipe elements are heated to a flat profile at 220 ° C., the speed of rotation of the screws being 60 rpm. For the counter examples of the invention based on polyamide 6/11, the pipe elements are heated to a flat profile at 180 ° C, the speed of rotation of the screws being 60 rpm.
Tests réalisés sur les films : Tests made on the films:
Test de reprise en eau : Water recovery test:
Le test de reprise en humidité consiste à mesurer le taux d'humidité obtenu à saturation dans un film de 400 μιη (micromètre) après un conditionnement réalisé en chaleur humide à 85°C et 85 % d'humidité relative (HR). La mesure du taux d'humidité est effectuée selon la méthode Karl-Fisher basée sur la norme ISO 15512. Pour mesurer le taux d'humidité absorbée, le film est soumis à une étape de désorption thermique sous azote pendant 20 minutes à 200°C.  The moisture recovery test consists in measuring the saturation humidity level obtained in a film of 400 μιη (micrometer) after conditioning done in moist heat at 85 ° C. and 85% relative humidity (RH). The humidity measurement is carried out according to the Karl-Fisher method based on the ISO 15512 standard. To measure the absorbed moisture content, the film is subjected to a thermal desorption step under nitrogen for 20 minutes at 200 ° C. .
Résultats de reprise en eau pour les différents échantillons : Water recovery results for the different samples:
Compositions Taux d'humidité (%) Compositions Moisture content (%)
Exemple 1 0,25  Example 1 0.25
Exemple 2 0,31  Example 2 0.31
Exemple 3 0,41  Example 3 0.41
Exemple 4 0,41  Example 4 0.41
Exemple 5 0,43  Example 5 0.43
Exemple 6 0,31  Example 6 0.31
Exemple 7 0,32  Example 7 0.32
Exemple 8 0,32  Example 8 0.32
Exemple 9 0,37  Example 9 0.37
Exemple 10 0,29  Example 10 0.29
Contre-exemple 1 0,20  Counter-example 1 0.20
Contre-exemple 2 0,54  Counterexample 2 0.54
Contre-exemple 3 0,60  Counter-example 3 0.60
Contre-exemple 4 0,58  Counterexample 4 0.58
Contre-exemple 5 0,45 Le tableau de résultat ci-dessus montre de façon schématique comment la composition selon l'invention a été établie. Un résultat supérieur à 0,50 % sur le test en reprise en eau est disqualifiant pour la composition, dans l'application en question ; étant entendu que pour un grand nombre d'autres applications, ce même seuil disqualifiant de 0,50 % pour ce test est susceptible de s'appliquer. Counterexample 5 0.45 The result table above shows schematically how the composition according to the invention has been established. A result greater than 0.50% on the water test is disqualifying for the composition, in the application in question; it being understood that for a large number of other applications, the same disqualifying threshold of 0.50% for this test is likely to apply.
Les domaines de composition préférés pour la composition selon l'invention ont été établis non seulement sur la base de ce test en reprise en eau mais également sur des tests de propriétés thermomécaniques tels qu'un test de fluage à 100°C, de MFI (« Melt Flow Index ») ainsi que sur des tests relatifs aux propriétés optiques (test de transparence, de jaunissement en vieillissement accéléré).  The preferred composition domains for the composition according to the invention were established not only on the basis of this test in water recovery but also on thermomechanical properties tests such as a 100 ° C creep test, MFI ( "Melt Flow Index") as well as tests relating to optical properties (transparency test, yellowing in accelerated aging).
Il a également été constaté que les formulations selon l'invention, à savoir les exemples de compositions 1 à 10, montrent d'excellentes propriétés adhésives sur verre, notamment après un test de vieillissement en chaleur humide à 85°C et 85% HR (« Humidity Rate » ou Taux d'Humidité).  It has also been found that the formulations according to the invention, namely the examples of compositions 1 to 10, exhibit excellent adhesive properties on glass, in particular after a wet heat aging test at 85 ° C. and 85% RH ( "Humidity Rate" or Humidity Rate).
II est important de noter que, contrairement au résultat plutôt satisfaisant concernant l'exemple comparatif 1, ce dernier est impropre à l'application car sa résistance au fluage est insuffisante.  It is important to note that, contrary to the rather satisfactory result concerning Comparative Example 1, it is unsuitable for application because its resistance to creep is insufficient.
L'exemple comparatif 4 est impropre à l'application car la reprise en humidité est trop élevée et la température de fusion du polyamide est inadaptée à l'application. Le produit ne s'écoule pas aux températures usuelles de fabrication des panneaux photovoltaïques.  Comparative Example 4 is unfit for application because the moisture recovery is too high and the melting temperature of the polyamide is unsuitable for the application. The product does not flow at the usual manufacturing temperatures of the photovoltaic panels.
L'exemple comparatif 5 est impropre à l'application car la température de fusion du polyamide est inadaptée à l'application. En effet, le produit ne s'écoule pas aux températures usuelles de fabrication des panneaux photovoltaïques.  Comparative Example 5 is unfit for application because the melting temperature of the polyamide is unsuitable for the application. Indeed, the product does not flow at the usual manufacturing temperatures of photovoltaic panels.

Claims

REVENDICATIONS
1. Composition thermoplastique comprenant au moins un mélange de trois polymères, dans laquelle : A thermoplastic composition comprising at least one mixture of three polymers, wherein:
- le premier polymère, présent dans la composition entre 10% et 70% en poids, consiste en un polymère greffé polyamide présentant un tronc en polyoléfme contenant un reste d'au moins un monomère insaturé (X) et une pluralité de greffons en polyamide, dans lequel : the first polymer, present in the composition between 10% and 70% by weight, consists of a polyamide graft polymer having a polyolefin trunk containing a residue of at least one unsaturated monomer (X) and a plurality of polyamide grafts, in which :
- les greffons en polyamide sont attachés au tronc en polyoléfme par le reste du monomère insaturé (X) comprenant une fonction capable de réagir par une réaction de condensation avec un polyamide ayant au moins une extrémité aminé et/ou au moins une extrémité acide carboxylique,  the polyamide grafts are attached to the polyolefin trunk by the remainder of the unsaturated monomer (X) comprising a function capable of reacting, by a condensation reaction, with a polyamide having at least one amine end and / or at least one carboxylic acid end,
- le reste du monomère insaturé (X) est fixé sur le tronc par greffage ou copo lymérisation,  the remainder of the unsaturated monomer (X) is attached to the trunk by grafting or copolymerization,
- les greffons en polyamide représentent de 10%> à 60%>, de préférence de 15% à the polyamide grafts represent from 10% to 60%, preferably from 15% to
55%), en poids dudit polymère greffé polyamide, 55%), by weight of said polyamide graft polymer,
- le second polymère, présent dans la composition entre 10 % et 90 % en poids, consiste en un copolymère d'éthylène et d'un comonomère non réactif ou non fonctionnalisé dont le module élastique en flexion est inférieur à 250 Mpa à 23°C et qui présente un point de fusion cristalline compris entre 60°C et 120°C,  the second polymer, present in the composition between 10% and 90% by weight, consists of a copolymer of ethylene and a non-reactive or non-functional comonomer whose flexural elastic modulus is less than 250 MPa at 23 ° C. and which has a crystalline melting point of 60 ° C to 120 ° C,
- le troisième polymère, présent dans la composition entre 3 % et 45 % en poids de ladite composition, consistant en une polyoléfme fonctionnalisée comprenant un copolymère d'au moins une alpha-oléfïne, telle que l'éthylène ou le propylène, avec au moins un comonomère portant une fonction réactive, et au moins un autre comonomère ne portant pas de fonction réactive, choisi parmi une alpha-oléfïne différente de la susdite alpha-oléfïne, un diène, un ester d'acide carboxylique insaturé, et un ester vinylique d'acide carboxylique, un anhydride d'acide dicarboxylique comme l'anhydride maléique,  the third polymer, present in the composition, between 3% and 45% by weight of said composition, consisting of a functionalized polyolefin comprising a copolymer of at least one alpha-olefin, such as ethylene or propylene, with at least a comonomer bearing a reactive function, and at least one other comonomer not carrying a reactive function, chosen from an alpha-olefin different from the aforesaid alpha-olefin, a diene, an unsaturated carboxylic acid ester, and a vinyl ester, carboxylic acid, a dicarboxylic acid anhydride such as maleic anhydride,
caractérisée en ce que les greffons en polyamide du susdit premier polymère présentent une température de transition vitreuse ainsi qu'une température de fusion inférieures ou égale à 160°C, et en ce que le taux des greffons polyamide dudit premier polymère représente de 3 % à 15 %, de préférence entre 5 % et 12,5 %, en poids de la composition thermoplastique. characterized in that the polyamide grafts of the above-mentioned first polymer have a glass transition temperature and a melting temperature of less than or equal to 160 ° C, and in that the level of the polyamide grafts of said first polymer is from 3% to 15%, preferably from 5% to 12.5%, by weight of the thermoplastic composition.
2. Composition selon la revendication 1, caractérisée en ce que le second polymère consiste en un copolymère de l'éthylène et d'un (méth)acrylate d'alkyle. 2. Composition according to claim 1, characterized in that the second polymer consists of a copolymer of ethylene and an alkyl (meth) acrylate.
3. Composition selon la revendication 1 ou 2, caractérisée en ce que la masse molaire en nombre des susdits greffons polyamide du susdit polymère greffé est comprise dans la gamme allant de 1000 à 10000 g/mol. 3. Composition according to claim 1 or 2, characterized in that the number-average molar mass of said polyamide grafts of said graft polymer is in the range of 1000 to 10000 g / mol.
4. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que, pour les susdits polymères greffés, le nombre de monomère (X) fixé sur le tronc en polyoléfme est supérieur ou égal à 1,3 et/ou inférieur ou égal à 20. 4. Composition according to any one of the preceding claims, characterized in that, for the aforementioned graft polymers, the number of monomer (X) attached to the polyolefin trunk is greater than or equal to 1.3 and / or less than or equal to at 20.
5. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que le susdit premier polymère est présent dans la composition entre 10% et 50% en poids. 5. Composition according to any one of the preceding claims, characterized in that the aforesaid first polymer is present in the composition between 10% and 50% by weight.
6. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que les greffons polyamide du premier polymère consistent en des copolyamides choisi parmi les copolyamides PA 6/1 1, PA6/12 et PA6/11/12. 6. Composition according to any one of the preceding claims, characterized in that the polyamide grafts of the first polymer consist of copolyamides chosen from copolyamides PA 6/1 1, PA6 / 12 and PA6 / 11/12.
7. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que le troisième polymère consiste en un copolymère éthylène - ester acrylique - méthacrylate de glycidyle ou éthylène - ester acrylique - anhydride maléique. 7. Composition according to any one of the preceding claims, characterized in that the third polymer consists of an ethylene-acrylic ester-glycidyl methacrylate or ethylene-acrylic ester-maleic anhydride copolymer.
8. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que le monomère insaturé (X) du premier polymère est un anhydride maléique. 8. Composition according to any one of the preceding claims, characterized in that the unsaturated monomer (X) of the first polymer is a maleic anhydride.
9. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que le second polymère est présent dans la composition entre dans la composition entre 40% et 70% en poids. 9. Composition according to any one of the preceding claims, characterized in that the second polymer is present in the composition between the composition between 40% and 70% by weight.
10. Composition selon la revendication 8, caractérisée en ce que le troisième polymère est présent entre 10%> et 30%> en poids dans la composition. 10. Composition according to claim 8, characterized in that the third polymer is present between 10% and 30% by weight in the composition.
11. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle consiste uniquement en les trois susdits polymères. 11. Composition according to any one of the preceding claims, characterized in that it consists solely of the three aforesaid polymers.
12. Film thermoplastique comprenant la composition selon l'une quelconque des revendications précédentes. Thermoplastic film comprising the composition of any one of the preceding claims.
13. Film thermoplastique d'un module photovoltaïque, ledit module photovoltaïque comprenant au moins deux couches dont l'une forme la couche d'encapsulant et/ou une couche arrière de protection, caractérisé en ce que la couche d'encapsulant comprend, de préférence consiste en, la composition thermoplastique selon l'une quelconque des revendications 1 à 11. 13. Thermoplastic film of a photovoltaic module, said photovoltaic module comprising at least two layers, one of which forms the encapsulant layer and / or a rear protective layer, characterized in that the encapsulant layer preferably comprises consists of the thermoplastic composition according to any one of claims 1 to 11.
14. Film selon la revendication 13, caractérisé en ce que la couche formant encapsulant comprend des promoteurs d'adhésion consistant en un ingrédient non polymérique, de nature organique, cristalline ou minéral et plus préférentiellement semi- minéral semi-organique, des antioxydants et/ou des agents anti-UVs. 14. Film according to claim 13, characterized in that the encapsulant layer comprises adhesion promoters consisting of a non-polymeric ingredient, of organic, crystalline or mineral nature and more preferably semi-inorganic semi-organic, antioxidants and / or or anti-UV agents.
EP14784502.8A 2013-09-24 2014-09-17 Thermoplastic composition, in particular for photovoltaic modules Active EP3049461B1 (en)

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FR1359174A FR3011001B1 (en) 2013-09-24 2013-09-24 THERMOPLASTIC COMPOSITION, IN PARTICULAR FOR PHOTOVOLTAIC MODULES
PCT/FR2014/052313 WO2015044560A1 (en) 2013-09-24 2014-09-17 Thermoplastic composition, in particular for photovoltaic modules

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WO2024126966A1 (en) * 2022-12-16 2024-06-20 Arkema France Multilayer structure with adhesive properties

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EP3049461B1 (en) 2018-11-21
FR3011001B1 (en) 2016-11-04
CN105722893B (en) 2019-07-23
CN105722893A (en) 2016-06-29
US9978897B2 (en) 2018-05-22
FR3011001A1 (en) 2015-03-27
JP2016533421A (en) 2016-10-27
US20160247953A1 (en) 2016-08-25
WO2015044560A1 (en) 2015-04-02
JP6605476B2 (en) 2019-11-13

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